In the absence of seven-time champion Rafael Nadal, ousted in the quarterfinals, the Serbian produced a near flawless performance on centre
court to defend his title and hand Federer his fourth final defeat in Rome.
With Roland Garros a little more than a week away, Djokovic could emerge as the favourite to claim what is an elusive title in the French capital,
especially in light of Nadal's current woes on clay.
The Spaniard has won only one title on the surface this year, at Buenos Aires, and been beaten by Italian Fabio Fognini, Andy Murray, Djokovic and Switzerland's Stan Wawrinka in recent tournaments.
Djokovic, meanwhile, has brought his game to boiling point this week to claim his fifth title of the season and take his head-to-head record over the
Swiss ace to 21-18.
On this performance, Djokovic will be hard to beat at the French Open, where Nadal's bid for a 10th title could be compounded by a lack of top
The Serbian traded blows with Federer from the opening stages and, at 5-4 ahead, converted his first break of the set with a return winner that clipped the edge of the tramline.
Federer was not without some choice shots of his own, the classy Swiss powering a backhand winner down the line to save a second break point in the second game of the second set.
But Djokovic's precision, power and pace looked unstoppable.
He took the early lead with a break for 2-0 and, after taking a three-game advantage behind a total of 30-12 baseline points won, was never in danger.
Djokovic secured his fourth Rome trophy in just 76 minutes as Federer struck a forehand wide on match point.
He proved to be less adept at handling the post-game celebration champagne, however, as this YouTube video shows: