World number one Djokovic, who swept past Federer in straight sets in the French Open semi-finals earlier this month, could meet the Swiss again in the last four.
The top-seeded Serb will start his campaign against Spain's former world number one Juan Carlos Ferrero while Federer, who has lost in the quarter-finals in the last two years, takes on another Spaniard, Albert Ramos.
Second seed Rafael Nadal, fresh from a record seventh French Open title, meets Brazil's Thomaz Bellucci.
Fourth-seeded Briton Andy Murray, who has lost in the semi-finals in the last two years to Nadal, is scheduled to meet the Spaniard again in the last four, but first he must get past wily Russian Nikolay Davydenko in his opener.
Lleyton Hewitt, the 2002 champion, begins against French star Jo-Wilfried Tsonga, who knocked out Federer in five sets in the quarter-finals last year.
Hewitt's Australian compatriot Bernard Tomic starts against Belgium's David Goffin who went through qualifying at the French Open and reached the fourth round where he took a set off Federer before losing in four.
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