Dimitrov earlier battled past Greek seventh seed Stefanos Tsitsipas (25) 6-3, 6-7, 7-6 to reach his second ATP Masters 1000 final, and first since 2017, and give himself the opportunity to snap a title drought stretching back six years.
Top seed Djokovic came into the contest with Rublev having defeated the Russian four times in five matches, including in the last three meetings, and he broke him in the opening game only to immediately hand back the advantage.
The 36-year-old Serbian laboured through his service games and saved three break points to remain in touch at 4-4 before surrendering the opening set with a failed drop shot while trailing 6-5.
"Rublev was suffocating me like a snake suffocates a frog for most of the match," Djokovic said.
"He was playing at an extremely high level. I knew that he possesses great quality but today he played off the charts. I don't think I've ever faced Rublev this good."
There was little to separate the duo in the next set until Djokovic raised his game in the tiebreak to level the contest with an ace out wide, before getting treatment on court for a lower back problem.
A rejuvenated Djokovic then grabbed the telling break in the 12th game of the deciding set after a double fault by Rublev to extend his winning run to 17 matches since his loss to Carlos Alcaraz (20) in the Wimbledon final.
"I was struggling a bit with my fitness at the beginning but went through it and it was crucial to win the second set. In the tiebreak I served very well and that helped," Djokovic said.
"In the third set I was always there... He came up with some big serves when he needed to. In the end the double fault was an unfortunate ending for him but I think I deserved it considering the effort and the fight I put in."
Earlier, Dimitrov produced some of his best tennis in the decider against Tsitsipas to seal only his second win over the Greek in eight matches and continue the trend of unseeded players enjoying deep runs in the tournament.
"There were no tears but I got very emotional," Dimitrov, who became the sixth unseeded finalist in the past eight years at Paris, said of his animated celebration following the win.
"I'm just living in the moment right now. It's been a funny road of late but each win means more and more to me."
