The tournament's top-seed and defending champion booked a spot in the final by defeating fellow Serbian Janko Tipsarevic 6-4, 6-1 on Saturday in a match that was delayed twice by rain.
Djokovic, ranked second in the world, is looking for his third title at the tournament and first trophy since winning four months ago in Miami. He will face the No. 14 seed Richard Gasquet, who eliminated eighth-seeded American John Isner 7-6 (3), 6-3 under cloudy skies earlier in the day at Rexall Centre.
Djokovic led 3-2 in the first set when umbrellas popped open in what's become a familiar sight at this week's tournament. It was the second delay of the match after the skies opened during the players' warmup, causing a 90-minute interruption.
"I don't see any reason why hard court tournament don't have covers on their courts," said Djokovic. "And I think this tournament, after this year's experience should strongly consider covers for next year. If they inflate the covers, like they do on Wimbledon for example, it saves us time.
"It would be a good solution to these problems."
When the match resumed after an hour, the two Serbs played a seesaw seventh game before Djokovic hit a stunning cross-court backhand, then won the game on Tipsarevic's unforced error to make it 4-4.
Long baseline rallies continued as both players chased the ball corner to corner. Djokovic finally broke through in the 10th game when the fifth-seed Tipsarevic went long twice from deuce to give his opponent the break and the set.
Tipsarevic, who had won two of their last three meetings, gave up another break early in the second set to go down 3-1, with Djokovic gaining momentum by wearing down his opponent with his return game. Djokovic broke again for a 5-1 lead, then served out for the match just under the stroke of midnight.
"I managed to play a good return game and when you're up a set up I felt momentum was on my side and that I should use it," said Djokovic. "And in the second set I played really good."
Gasquet, ranked 21st in the world, is making his first trip to a Masters 1000 final in six years. In 2006, also in Toronto, Gasquet lost to Roger Federer.
The 26-year-old handled Isner's imposing serve well, drawing the six-foot-nine American into a game of baseline rallies. He also served with precision, winning 90 per cent of first serve points in the first set, and finishing the match with four aces.
"It's a difficult player but the key to the match was to return well and I did it," said Gasquet. "I try to return all the time and make him play."
He blazed a backhand by Isner to lead 4-2 in the tiebreaker and smashed an overhead shot to close out the set and deflate Isner, who played two matches on Friday night because of rain delays. Gasquet also played two matches on Friday.
"I had to do a big tiebreak and I did it," said Gasquet. "And then I felt well, more confident. I felt more fresh after winning the first set."
Gasquet took control in the second set when he broke for a 5-2 lead. Isner double faulted on a deuce, then netted to give Gasquet the advantage, which he capitalized on with another backhand winner.
"It's tough. It's a world class (backhand)," said Isner. "It's just a gift. It's tough for me because I like to take the majority of my shots if I'm playing a righty to his backhand, and he was able to handle that pretty well.
"He was just a lot better than me today and he deserved the win. He was the better player in all facets."
The 27-year-old Isner, making his debut at the Toronto tournament, advanced to the semifinals by ousting Milos Raonic of Thornhill, Ont.
There are no Canadians left on the men's side. Top-ranked doubles specialist Daniel Nestor of Toronto and partner Max Mirnyi of Belarus lost their quarter-final match 6-4, 6-4 to Spain's Marcel Granollers and Marc Lopez on Saturday.
Granollers and Marc Lopez had their semi against Sweden's Robert Lindstedt and Horia Tecau of Romania postponed due to rain, as did Americans Bob and Mike Bryan and their match against Austria's Jurgen Melzer and India's Leander Paes.