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Sanchez, whose team has been decimated by crashes, had been part of an 11-man break which built a 16-minute lead on the peloton well before the end of the 191km stage from Limoux to Foix.
And after counter-attacking Frenchman Sandy Casar on the 38 km descent towards the finish, the Spaniard made a decisive move with just over 11km to race.
Sanchez went on unchallenged to finish 47sec ahead of Slovakian Peter Sagan (Liquigas) with FDJ rider Casar in third and the main peloton, including race leader Bradley Wiggins, coming over the finish 18 minutes in arrears.
"I started the day with victory in mind but given the company I was in I knew I'd have to attack from far out to have any chance," said Sanchez, whose team has only four remaining members from the nine starters.
Although the early breakaway had built a significant lead that never looked under threat, they were given further room by the dramatics going on in their wake - and which showed Wiggins' sense of fair play.
Defending champion Cadel Evans started the day 3min 19sec adrift but could have finished it far worse off after falling victim to several mechanical problems that left his hi-tech BMC team looking amateurish.
It later transpired that "one or two" spectators had thrown nails on to the road, causing a rash of punctures among the 50-strong chasing group according to race director Jean-Francois Pescheux.
First, the Australian was left waiting at the summit of the last, brutal climb, the Peguere, for nearly two minutes after suffering a problem with his back wheel.
Looking flustered and gesturing in despair as he held his bike minus its back wheel, he got a replacement from a team-mate only to require another wheel change on the descent, during which time the yellow jersey peloton had sat up and waited.
Even Wiggins had to change bike, the Englishman signalling to his team car to stop as he got a quick replacement.
It left Evans in a desperate chase with his BMC team to catch Wiggins' leading group, and he was glad once he did.
Pescheux later explained: "One or two spectators had thrown nails on to the road, we don't know why, but there were around 30 punctures altogether."
"The nails were mainly thrown on the ground around 200 metres from the summit.
"At the end, some riders ended up with two or three nails in their tyres."
Wiggins, who took the yellow jersey after stage seven last Saturday, will take a 2:05 lead over teammate Chris Froome into Monday's mainly flat stage from Samatan to Pau.
Italian Vincenzo Nibali (Liquigas) is still third overall at 2:23 with Evans still fourth at 3:19.
Results from the 14th stage of Tour de France, a 191km ride from Limoux to Foix on Sunday:
1. Luis Leon Sanchez (ESP/RAB) 4h50min 29sec
(average: 39.5 km/h)
2. Peter Sagan (SVK/LIQ) at 0:47.
3. Sandy Casar (FRA/FDJ) 0:47.
4. Philippe Gilbert (BEL/BMC) 0:47.
5. Gorka Izagirre (ESP/EUS) 0:47.
6. Sergio Paulinho (POR/SAX) 2:51.
7. Sebastien Minard (FRA/ALM) 2:51.
8. Martin Velits (SVK/OPQ) 3:49.
9. Eduard Vorganov (RUS/KAT) 4:51.
10. Steven Kruijswijk (NED/RAB) 4:53.
11. Cyril Gautier (FRA/EUC) 14:53.
12. Luis Angel Mate (ESP/COF) 18:15.
13. Julien Simon (FRA/SAU) 18:15.
14. Mickael Cherel (FRA/ALM) 18:15.
15. Bradley Wiggins (GBR/SKY) 18:15.
16. Cadel Evans (AUS/BMC) 18:15.
17. Vincenzo Nibali (ITA/LIQ) 18:15.
18. Kristjan Koren (SLO/LIQ) 18:15.
19. Brice Feillu (FRA/SAU) 18:15.
20. Chris Froome (GBR/SKY) 18:15.
21. Johnny Hoogerland (NED/VAC) 18:15.
22. Christian Knees (GER/SKY) 18:15.
23. Matthieu Ladagnous (FRA/FDJ) 18:15.
24. Chris Anker Sorensen (DEN/SAX) 18:15.
25. Edvald Boasson Hagen (NOR/SKY) 18:15.
26. Davide Malacarne (ITA/EUC) 18:15.
27. Haimar Zubeldia (ESP/RSH) 18:15.
28. Nicolas Roche (IRL/ALM) 18:15.
29. Jurgen Van den Broeck (BEL/LTB) 18:15.
30. Michael Rogers (AUS/SKY) 18:15.
31. Michael Schr (SUI/BMC) 18:15.
32. Richie Porte (AUS/SKY) 18:15.
33. Janez Brajkovic (SLO/AST) 18:15.
34. Francis de Greef (BEL/LTB) 18:15.
35. Maxime Monfort (BEL/RSH) 18:15.
36. Pierre Rolland (FRA/EUC) 18:15.
37. Maxime Bouet (FRA/ALM) 18:15.
38. Rui Costa (POR/MOV) 18:15.
39. Jerome Coppel (FRA/SAU) 18:15.
40. Amal Moinard (FRA/BMC) 18:15.
41. Frank Schleck (LUX/RSH) 18:15.
42. Thibaut Pinot (FRA/FDJ) 18:15.
43. Manuel Quinziato (ITA/BMC) 18:15.
44. George Hincapie (USA/BMC) 18:15.
45. Andriy Grivko (UKR/AST) 18:15.
46. Federico Canuti (ITA/LIQ) 18:15.
47. Michele Scarponi (ITA/LAM) 18:15.
48. Sylvester Szmyd (POL/LIQ) 18:15.
49. Fredrik Kessiakoff (SWE/AST) 18:15.
50. Tejay Van Garderen (USA/BMC) 18:15.
51. Denis Menchov (RUS/KAT) 18:15.
52. Yaroslav Popovych (UKR/RSH) 18:15.
53. Adam Hansen (AUS/LTB) 18:15.
54. Chris Horner (USA/RSH) 18:15.
55. Andreas Kloden (GER/RSH) 18:15.
56. Marcus Burghardt (GER/BMC) 18:15.
57. Dmitriy Fofonov (KAZ/AST) 18:15.
58. Ivan Basso (ITA/LIQ) 18:15.
59. Juan Jose Cobo Acebo (ESP/MOV) 18:15.
60. Peter Velits (SVK/OPQ) 18:15.
61. Alejandro Valverde (ESP/MOV) 18:15.
62. Pieter Weening (NED/GEC) 18:15.
63. Jelle Vanendert (BEL/LTB) 18:15.
64. Egoi Martinez (ESP/EUS) 18:15.
65. Andrei Kashechkin (KAZ/AST) 18:15.
66. Vladimir Karpets (RUS/MOV) 18:15.
67. Daniel Oss (ITA/LIQ) 18:15.
68. Levi Leipheimer (USA/OPQ) 18:15.
69. Thomas Voeckler (FRA/EUC) 18:27.
70. Jens Voigt (GER/RSH) 21:19.
71. Anthony Roux (FRA/FDJ) 21:19.
72. Arthur Vichot (FRA/FDJ) 21:19.
73. Ruben Perez Moreno (ESP/EUS) 21:19.
74. Nicki Sorensen (DEN/SAX) 21:19.
75. Nicolas Edet (FRA/COF) 21:19.
76. Daniel Martin (IRL/GRM) 21:19.
77. Jean Christophe Peraud (FRA/ALM) 21:19.
78. Pierrick Fedrigo (FRA/FDJ) 21:19.
79. Simone Stortoni (ITA/LAM) 21:19.
80. Vladimir Gusev (RUS/KAT) 21:19.
81. Giampaolo Caruso (ITA/KAT) 21:19.
82. Samuel Dumoulin (FRA/COF) 23:33.
83. Laurens ten Dam (NED/RAB) 23:33.
84. Jorge Azanza (ESP/EUS) 23:33.
85. Stephen Cummings (GBR/BMC) 26:01.
86. Yury Trofimov (RUS/KAT) 26:01.
87. Guillaume Levarlet (FRA/SAU) 26:01.
88. Fabrice Jeandesboz (FRA/SAU) 26:01.
89. Kevin De Weert (BEL/OPQ) 26:01.
90. Marco Marzano (ITA/LAM) 26:01.
91. Luca Paolini (ITA/KAT) 26:01.
92. Albert Timmer (NED/ARG) 28:18.
93. Jerome Pineau (FRA/OPQ) 28:18.
94. Roy Curvers (NED/ARG) 28:18.
95. Christophe Riblon (FRA/ALM) 28:18.
96. Blel Kadri (FRA/ALM) 28:18.
97. Sylvain Chavanel (FRA/OPQ) 28:18.
98. Cedric Pineau (FRA/FDJ) 28:18.
99. Jeremy Roy (FRA/FDJ) 28:18.
100. Koen de Kort (NED/ARG) 28:18.
101. Marco Marcato (ITA/VAC) 28:18.
102. Borut Bozic (SLO/AST) 28:18.
103. Bert Grabsch (GER/OPQ) 28:18.
104. Patrick Gretsch (GER/ARG) 28:18.
105. Romain Zingle (BEL/COF) 28:18.
106. Sebastien Hinault (FRA/ALM) 28:18.
107. Nick Nuyens (BEL/SAX) 28:18.
108. Dominik Nerz (GER/LIQ) 28:18.
109. Greg Henderson (NZL/LTB) 28:18.
110. Simon Gerrans (AUS/GEC) 28:18.
111. Baden Cooke (AUS/GEC) 28:18.
112. Lars Ytting Bak (DEN/LTB) 28:18.
113. Anders Lund (DEN/SAX) 28:18.
114. Rafael Valls (ESP/VAC) 28:18.
115. Kenny van Hummel (NED/VAC) 28:18.
116. Ruben Plaza (ESP/MOV) 28:18.
117. Daryl Impey (RSA/GEC) 28:18.
118. Yauheni Hutarovich (BLR/FDJ) 28:18.
119. Andre Greipel (GER/LTB) 28:18.
120. Jurgen Roelandts (BEL/LTB) 28:18.
121. Marcel Sieberg (GER/LTB) 28:18.
122. Jimmy Engoulvent (FRA/SAU) 28:18.
123. Michael Morkov (DEN/SAX) 28:18.
124. Giovanni Bernaudeau (FRA/EUC) 28:18.
125. Rein Taaramae (EST/COF) 28:18.
126. Yukiya Arashiro (JPN/EUC) 28:18.
127. Alessandro Vanotti (ITA/LIQ) 28:18.
128. Pablo Urtasun (ESP/EUS) 28:18.
129. Julien Fouchard (FRA/COF) 28:18.
130. Tyler Farrar (USA/GRM) 28:18.
131. Cyril Lemoine (FRA/SAU) 28:18.
132. Juan Jose Haedo (ARG/SAX) 28:18.
133. Jan Ghyselinck (BEL/COF) 28:18.
134. Vasil Kiryienka (BLR/MOV) 28:18.
135. Christian Vande Velde (USA/GRM) 28:18.
136. Danilo Hondo (GER/LAM) 28:18.
137. Jean-Marc Marino (FRA/SAU) 28:18.
138. Grega Bole (SLO/LAM) 28:18.
139. Mathieu Sprick (FRA/ARG) 28:18.
140. Yann Huguet (FRA/ARG) 28:18.
141. Jonathan Cantwell (AUS/SAX) 28:18.
142. Matthew Goss (AUS/GEC) 28:18.
143. David Millar (GBR/GRM) 28:18.
144. Stuart O'Grady (AUS/GEC) 28:18.
145. Dries Devenyns (BEL/OPQ) 28:18.
146. Johan Van Summeren (BEL/GRM) 28:18.
147. David Zabriskie (USA/GRM) 28:18.
148. Mark Cavendish (GBR/SKY) 28:18.
149. Maxim Iglinskiy (KAZ/AST) 28:18.
150. Joan Horrach (ESP/KAT) 28:18.
151. Alexander Vinokourov (KAZ/AST) 28:18.
152. Aliaksandr Kuschynski (BLR/KAT) 28:18.
153. Karsten Kroon (NED/SAX) 28:18.
154. Michael Albasini (SWI/GEC) 28:18.
155. Bram Tankink (NED/RAB) 28:18.
156. Sebastian Langeveld (NED/GEC) 28:18.
157. Brett Lancaster (AUS/GEC) 28:18.
158. Bernhard Eisel (AUT/SKY) 28:18.
159. Yohann Gene (FRA/EUC) 28:30.
160. Vincent Jerome (FRA/EUC) 28:30.
161. Kris Boeckmans (BEL/VAC) 28:30.
162. Christophe Kern (FRA/EUC) 31:53.
. Robert Kiserlovski (CRO/AST) Retired
