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The 2004 Wimbledon champion was given a stern test by France's up-and-coming Kristina Mladenovic but the Russian third seed eventually triumphed in a 7-6 (7/5), 6-3 win on Centre Court.
"I'm really pleased with this performance," Sharapova said.
"My opponent played extremely well so I'm really happy to be in the second round.
"I knew that my opponent was capable of playing really great tennis. I tried to take my opportunities in the tie-break.
"I was happy with the way I stepped up in the second set. It's always nice when you're not breaking somebody to get ahead and win that tie breaker.
"It was still pretty tough in the end but I'm glad I got it done in two."
With the top 32 players seeded and kept apart until the third round at the earliest, Sharapova could scarcely have had a tougher first round draw.
Mladenovic, the Wimbledon 2009 girls' runner-up, is on a career-high world ranking of 37 and showed why she is tipped as one to watch for the future.
Sharapova was pushed hard by Mladenovic in the first set, who matched her illustrious opponent in both her serves and groundstrokes.
And the French number three had had the set's only break point going into the tie-break.
At 5-5, Sharapova remonstrated at length with the umpire, who gave Mladenovic a let following a correct challenge by the Frenchwoman.
Though the Russian went on to lose the game, she did not let it affect her focus, taking the next game to love to set up the tie-break.
Sharapova held serve to give herself set point and won it with a high backhand at the end of a scrappy point at the net.
Mladenovic held off a string of break points in the first game of the second set but Sharapova's grit eventually saw her through into the second round.
The build-up to Wimbledon was dominated by a very public spat between Sharapova and world number one Williams, who beat the Russian in the French Open final.
Sharapova blasted the defending champion for her controversial comments over a high-profile rape case and a perceived slight against her relationship with Bulgarian player, Grigor Dimitrov.
Laying bare the bitter rivalry between the two, the Siberian dished some back, ripping into the American's colourful private life and telling Williams to keep her opinions to herself.
With Mladenovic seen off, Sharapova faces either Portuguese qualifier Michelle Larcher de Brito or Melanie Oudin of the United States in the second round.
Results on the first day of Wimbledon (x denotes seeded player):
Men's singles:
First round:
Steve Darcis (BEL) bt Rafael Nadal (ESP x5) 7-6 (7/4), 7-6 (10/8), 6-4
Lukasz Kubot (POL) bt Igor Andreev (RUS) 6-1, 7-5, 6-2
Stephane Robert (FRA) bt Alejandro Falla (COL) 6-3, 7-6 (7/5), 7-5
Benot Paire (FRA x25) bt Adrian Ungur (ROM) 6-4, 4-6, 6-3, 6-1
John Isner (USA x18) bt Evgeny Donskoy (RUS) 6-1, 7-6 (7/5), 7-6 (7/3)
Adrian Mannarino (FRA) bt Pablo Andjar (ESP) 6-1, 6-2, 6-3
Dustin Brown (GER) bt Guillermo Garca-Lpez (ESP) 6-3, 6-3, 6-3
Lleyton Hewitt (AUS) bt Stanislas Wawrinka (SUI x11) 6-4, 7-5, 6-3
Nicolas Almagro (ESP x15) bt Jurgen Zopp (EST) 6-4, 7-6 (7/2), 7-5
Guillaume Rufin (FRA) bt Marinko Matosevic (AUS) 6-1, 4-6, 6-4, 6-3
Radek Stepanek (CZE) bt Matt Reid (AUS) 6-2, 6-2, 6-4
Jerzy Janowicz (POL x24) bt Kyle Edmund (GBR) 6-2, 6-2, 6-4
Jurgen Melzer (AUT) bt Fabio Fognini (ITA x30) 6-7 (5/7), 7-5, 6-3, 6-2
Julian Reister (GER) bt Luks Rosol (CZE) 6-3, 4-6, 7-6 (7/5), 6-7 (4/7), 6-4
Sergiy Stakhovsky (UKR) bt Rogrio Dutra Silva (BRA) 6-4, 6-0, 6-4
Roger Federer (SUI x3) bt Victor Hanescu (ROM) 6-3, 6-2, 6-0
Jo-Wilfried Tsonga (FRA x6) bt David Goffin (BEL) 7-6 (7/4), 6-4, 6-3
Ernests Gulbis (LAT) bt Edouard Roger-Vasselin (FRA) 7-6 (7/1), 6-4, 7-5
Fernando Verdasco (ESP) bt Xavier Malisse (BEL) 6-7 (5/7), 6-1, 6-4, 6-3
Julien Benneteau (FRA x31) bt Tobias Kamke (GER) 6-4, 6-7 (5/7), 6-4, 6-2
Juan Monaco (ARG x22) bt Bastian Knittel (GER) 6-4, 6-2, 6-3
Rajeev Ram (USA) bt Luks Lacko (SVK) 7-5, 6-4, 6-7 (2/7), 6-2
Kenny De Schepper (FRA) bt Paolo Lorenzi (ITA) 7-6 (8/6), 6-4, 6-2
Marin Cilic (CRO x10) bt Marcos Baghdatis (CYP) 6-3, 6-4, 6-4
Viktor Troicki (SRB) bt Janko Tipsarevic (SRB x14) 6-3, 6-4, 7-6 (7/5)
Andrey Kuznetsov (RUS) bt Albert Montas (ESP) 6-3, 6-4, 3-6, 6-3
Vasek Pospisil (CAN) bt Marc Gicquel (FRA) 6-3, 6-2, 7-6 (7/3)
Mikhail Youzhny (RUS x20) bt Robin Haase (NED) 6-4, 7-5, 7-5
Tommy Robredo (ESP x32) bt Alex Bogomolov Jr. (RUS) 6-2, 6-2, 6-4
Nicolas Mahut (FRA) bt Jan Hjek (CZE) 6-2, 6-4, 6-3
Lu Yen-Hsun (TPE) bt James Ward (GBR) 6-7 (4/7), 6-4, 7-6 (13/11), 7-6 (7/4)
Andy Murray (GBR x2) bt Benjamin Becker (GER) 6-4, 6-3, 6-2
Women's singles:
First round:
Monica Puig (PUR) bt Sara Errani (ITA x5) 6-3, 6-2
Silvia Soler (ESP) bt Misaki Doi (JPN) 1-6, 6-4, 6-1
Lesya Tsurenko (UKR) bt Lara Arruabarrena (ESP) 6-1, 6-3
Eva Birnerov (CZE) bt Varvara Lepchenko (USA x26) 6-2, 4-6, 6-4
Sloane Stephens (USA x17) bt Jamie Hampton (USA) 6-3, 6-3
Andrea Petkovic (GER) bt Pauline Parmentier (FRA) 6-3, 6-2
Petra Cetkovsk (CZE) bt Donna Vekic (CRO) 6-3, 6-1
Caroline Wozniacki (DEN x9) bt Estrella Cabeza (ESP) 6-0, 6-2
Marion Bartoli (FRA x15) bt Elina Svitolina (UKR) 6-3, 7-5
Christina McHale (USA) bt Alexa Glatch (USA) 6-4, 6-4
Camila Giorgi (ITA) bt Samantha Murray (GBR) 6-3, 6-4
Sorana Cirstea (ROM x22) bt Stefanie Vgele (SUI) 7-5, 7-6 (7/3)
Lucie Safarova (CZE x27) bt Lauren Davis (USA) 6-4, 6-0
Karin Knapp (ITA) bt Lucie Hradeck (CZE) 6-3, 6-4
Michelle Larcher de Brito (POR) bt Melanie Oudin (USA) 7-6 (9/7), 1-6, 6-4
Maria Sharapova (RUS x3) bt Kristina Mladenovic (FRA) 7-6 (7/5), 6-3
Petra Kvitova (CZE x8) bt Coco Vandeweghe (USA) 6-1, 5-7, 6-4
Yaroslava Shvedova (KAZ) bt Kiki Bertens (NED) 6-4, 6-3
Garbie Muguruza (ESP) bt Anne Keothavong (GBR) 6-4, 6-0
Ekaterina Makarova (RUS x25) bt Johanna Larsson (SWE) 6-3, 6-3
Carla Surez (ESP x19) bt Lourdes Domnguez (ESP) 6-2, 6-2
Mirjana Lucic (CRO) bt Sofia Arvidsson (SWE) 6-1, 6-4
Eugnie Bouchard (CAN) bt Galina Voskoboeva (KAZ) 5-7, 7-6 (7/5), 6-4
Ana Ivanovic (SRB x12) bt Virginie Razzano (FRA) 7-6 (7/1), 6-0
Jelena Jankovic (SRB x16) bt Johanna Konta (GBR) 6-2, 7-5
Vesna Manasieva (SRB) bt Yanina Wickmayer (BEL) 3-6, 6-2, 6-4
Bojana Jovanovski (SRB) bt Ajla Tomljanovic (CRO) 3-6, 6-1, 9-7
Kirsten Flipkens (BEL x20) bt Yulia Putintseva (KAZ) 7-5, 6-4
Alize Cornet (FRA x29) bt Vania King (USA) 4-6, 6-3, 6-1
Su-Wei Hsieh (TPE) bt Tatjana Malek (GER) 6-1, 6-0
Flavia Pennetta (ITA) bt Elena Baltacha (GBR) 6-4, 6-1
Victoria Azarenka (BLR x2) bt Maria Joo Koehler (POR) 6-1, 6-2
