The 2009 U.S. Open champion set up a third-round clash with Taiwan's world No. 79 Yen-Hsun Lu by beating Slovenia's Blaz Kavcic 6-4 7-5 6-3, continuing his career revival following longterm wrist injury.
Third seed Andy Murray saved five break points on his way to a 6-3 6-2 victory over Taiwan's Yen-Hsun Lu, avenging his defeat to the world No. 79 at the Beijing 2008 Olympics.
Richard Gasquet is up next for Djokovic after the Frenchman's 6-4 3-6 6-4 win over compatriot and 15th seed Gael Monfils, while Federer will face the winner of Seppi's clash with Taiwan's Yen-Hsun Lu.