Djokovic, who came up empty in five prior Cincinnati finals, defeated seven-time victor Roger Federer 6-4, 6-4 in the final.
Former world number one Novak Djokovic became the first player to win all nine Masters 1,000 tournaments with victory over Roger Federer in Cincinnati.
Federer, a seven-time champion in Cincinnati, lost a final in the hardcourt US Open tuneup for the first time.
Djokovic applied the pressure in the opening game of the match, but second seed Federer saved two break points after being forced back as his rival found his range immediately.More news: Winx beats Black Caviar's record with 26th straight win
The Wimbledon champion is the first to claim the Career Golden Masters, having won all nine titles in the elite series that began in 1990.
"Thank you for letting me win once in Cincinnati", Djokovic said to Federer.
"It's been a great week, tough on the players but we had a fun time".
Federer was given a warning after venting his fury following that rare air shot and Djokovic served out the set in 37 minutes after losing just four points on serve.
Federer was making too many errors and Djokovic refused to allow him a way back, the Swiss spraying a forehand wide under pressure after being pushed back to spark exuberant celebrations from 13-time major victor and history maker.More news: Air quality to worsen as smoke returns
Federer fought back in the second and he broke Djokovic in the second game but his opponent responded by breaking straight back.
"Missing every second serve on the forehand side, I don't know what that was about".
"Wonderful feeling" The Serb now leads Federer 24-22 and has won their last three encounters.
"Novak totally deserved to win today".
Djokovic broke that streak to go up 4-3 in the opening set, prompting Federer to mutter angrily.More news: EU`s relief fund for Lombok earthquakes reaches U.S. $1.4 million