Despite Federer’s 17 Grand Slam titles, an Olympic singles medal has so far eluded him, although he won gold in the men’s doubles in 2008.
Federer took back the top spot from Djokovic last month after winning Wimbledon, where the Olympic tennis will also be played.
“Roger Federer is a recent Wimbledon winner and stands the best chance to win gold because of his career of success,” Djokovic said.
He said Britain’s Andy Murray could also win at his home Olympics.
“Then you have Andy Murray, Jo-Wilfried Tsonga and myself,” Djokovic said.
Reigning Olympic champion Rafael Nadal is injured and unable to take part.
Djokovic won Wimbledon last year and has reached the semifinals on three other occasions, most recently last month, losing to Federer in the semfinals.