The 29-year-old was greeted by a throng of fans and journalists at the Tom Jobim airport arrivals hall late on Monday afternoon, reports Xinhua.
Djokovic told reporters he was looking forward to the "experience of a lifetime" at the Athletes' Village in Rio's west.
"In Beijing we were all together. In London I stayed in an apartment near Wimbledon," Djokovic told reporters. "I'm excited about being close to other athletes, share our experiences, have lunch together. It will be the experience of a lifetime."
Djokovic took bronze at the Beijing 2008 Games and just missed out on a medal at the London 2012 Games, where he was the Serbian team's flag bearer.
He was beaten by eventual champion Andy Murray in the semi-finals and lost the bronze medal match against Juan Martin Del Potro.
The winner of 12 Grand Slam titles warmed up for the August 5-21 Olympics by defeating Kei Nishikori 6-3, 7-5 in the Toronto Masters final on Sunday.
He said he was hopeful Serbia's Olympic team would eclipse their tally of four medals in London.
"There are more Serbians competing, which shows that we are getting better. We are all hoping to get to the final. We are here to enjoy this great event and fight for a medal," he said.
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