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Home riders Igor Anton and Joaquim Rodriguez were given the same time at the top of the standings after the mountain leg was won by Frenchman David Moncoutie of the Cofidis team.
Rodriguez, of the Katusha team, was initially informed he was the race leader but better results in previous stages meant Anton was eventually awarded the red jersey.
"I'm as surprised as anybody I got the lead," Anton told reporters. "I thought Joaquim would get it after we dropped (overnight leader Philippe) Gilbert but I'm not complaining.
"I've no idea whether I can win overall. I've never won any kind of stage race, not even a small one, but I'll certainly defend this lead as best I can," added the Euskaltel-Euskadi rider after ending up seventh in the stage.
Part of an early break of five riders, Moncoutie attacked on a brutally steep ascent close to the finish deep in the mountain sierras of Alicante to claim the third Tour of Spain stage win of his career.
Spain's Serafin Martinez was second, 54 seconds back, with Johann Tschopp of Switzerland third.
Moncoutie crossed the line waving three fingers in the air to celebrate his hat-trick of victories.
"I lost time deliberately on a flat stage into Murcia so the overall contenders wouldn't worry about me getting in a break," he said.
"Now I'll concentrate on going for a third overall win in the King of the Mountains competition."
Moncoutie dedicated his success to Team Sky assistant Txema Gonzalez, 43, who died on Friday, and double Tour de France winner Laurent Fignon, 50, who passed away earlier this week.
Sky pulled out of the race following Gonzalez's death.
The race ends in Madrid on Sept. 19.
