Having lost the first set, Nadal could ill afford handing Djokovic a lead in the second, but his forehand continued to misfire and the Serb took the invitation to seize complete control with another break of serve.
Djokovic looked to be running away with it and moved in for the kill, but Nadal’s pride dug him out of a deep hole.
The Spaniard saved match point at 5-3 and again when he chased down a drop-shot at 5-4, but Djokovic merely sucked in some air, stared down the other end and blasted down his sixth ace, before clinching victory when Nadal sent a forehand wide.
While there was disappointment for Nadal, compatriots Fernando Verdasco and David Marrero gave Spain a lift with victory over Bob and Mike Bryan in the doubles final.
Verdasco and Marrero, the sixth seeds, upset the favorites 7-5, 6-7 (3/7), 10-7 as the title went to a Spanish pair for the second successive year following the triumph of Marcel Granollers and Mark Lopez 12 months ago.
The Californian Bryan twins were looking to win their 12th title of the year and surpass the 11 they won in 2007 and 2010, but were edged out in a match tiebreak.