"It's definitely one of the most special moments of my career," Djokovic said Sunday after defeating seven-time champion Federer 6-4, 6-4 in the Cincinnati Masters final.
His return to the top of tennis continues apace. He's now up to six in the world rankings after sinking to as low as 22 earlier this year because of injury.
"Obviously when I won the last point that's when I felt a huge relief but also great, great satisfaction," the Serb added.
The former world number one was desperate to win after losing in five prior Cincinnati finals.
"This is a dream come true," Djokovic said. "I finally won Cincinnati after six finals, some against the greatest ever, Roger."
Federer, a 20-time Grand Slam winner, said that although his game wasn't sharp he didn't want to take anything away from Djokovic's achievement.
"Novak is a great champion," Federer said. "This is about him making history."
The 37-year-old Swiss had been aiming for a 99th career trophy, but was unable to get over the line due in part to four double-faults at the most inopportune of times.
Djokovic claimed the opening set in 37 minutes and came back from an early break in the second to overhaul his long-time rival as they played for the 46th time.
The Serb now leads Federer 24-22 and has won their last three encounters.
"You know being the only player in history to win all Masters and Slams, you know it's definitely something that I'll be very, very proud of the rest of my life," he said.