While defending champion Federer will aim for a record-extending seventh title in the ATP Tour tournament, world No. 1 Djokovic will attempt to become the first singles player to win a complete collection of Masters 1000 titles.
The Serbian has lost four finals in the American city, which hosts one of the nine top-level tour events.
Federer beat him in 2009 and 2012, and on Saturday Djokovic came close to a repeat of last year's shock exit.
He was beaten in the third round 12 months ago on the hard courts by Spanish clay specialist Tommy Robredo, and this time was just two points away from losing to 66th-ranked Alexandr Dolgopolov in the semis.
Djokovic rallied, however, to triumph 4-6 7-6 (7-5) 6-2 against a player who came through the qualifying draw.
"He just plays more carefully on the big points," said the Ukrainian, whose resistance fell away in the final set as he needed medical treatment.
"You have to beat him and go for the risk. I really believed I can win and my game is enough to beat him. It was just the situation -- those few points decided everything."
Djokovic reached his 25th Masters final, and will be seeking his 20th title since the beginning of 2011.
The nine-time grand slam winner failed to complete a coveted major collection when he lost to Stan Wawrinka in June's French Open final.
He will be up against the man he denied a record-extending eighth Wimbledon title in July's final.
Federer, who's unbeaten in Cincinnati finals since winning his first in 2005, progressed after defeating Andy Murray 6-4 7-6 (8-6) in Saturday's second semi.
If he beats Djokovic, the 17-time grand slam champion will reclaim the world No. 2 ranking from last week's Montreal Masters victor Murray ahead of the U.S. Open starting August 31.
"That is not the story," Federer said after beating Murray. "It's whether Novak can make history by winning the 'Golden Masters.' I will try to stop that and win my seventh title."
The Swiss veteran has won seven of the nine Masters events, as has Andre Agassi and Rafael Nadal.
In men's doubles, American brothers Mike and Bob Bryan have a complete set, as does Canada's Daniel Nestor.