Djokovic will line up in a revenge repeat of last week's losing quarterfinal in Toronto when he takes on Andy Murray.
Despite his loss and whatever happens at the Beijing Olympics, Nadal will take over the top ranking from Federer on Aug 18 as computer points drop off.
Djokovic, the Australian Open champion and winner of two Masters shields already this season, will climb to second in the 2008 season points race.
Djokovic ripped off from a standing start, reaching a 5-0 lead after just 19 minutes before second seed Nadal got on the scoreboard. The Serb won the opener in 25 minutes, with 11 winners versus only two for Nadal.
Djokovic, who won the first eight points of the evening, lost only four points on serve in the opening phase.
Nadal lifted slightly in the second set, but Djokovic answered by saving the lone break point he faced in the sixth game to level 3-3.
The third seed ended that game with his fifth ace after coming from 0-30 and broke Nadal in the penultimate game of the match.
"I feel happy because for sure I will be number one," said Nadal. "It's been hard work for a long, long time.
"But there's no time to enjoy. I have Olympics in one week."
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