The newly-crowned world number one has been the story of the season so far.
He won his first 41 matches of the year - a run of 43 wins in a row overall - before coming unstuck against Roger Federer in the semi-finals of the French Open. It left him agonisingly short of Guillermo Vilas' record of 46 consecutive victories.
Djokovic's winning streak brought him eight titles, including Grand Slam crowns in Melbourne and Wimbledon, while it has also seen him leapfrog former world number on Rafael Nadal to the top ranking.
The 24-year-old Serb has previous Olympic Games experience having claimed a bronze medal at Beijing in 2008.
Seeded third in singles, Djokovic lost in the semi-finals to Nadal, 6-4 1-6 6-4 before defeating American James Blake, the loser of the other semi-final, in the bronze medal match 6-3 7-6.
He and Nenad Zimonjiæ, seeded second in men's doubles, were eliminated in the first round of the doubles by the Czech pairing of Martin Damm and Pavel Vízner.
He has been superb from the baseline this year with his defence challenging Nadal's as the best in the game. He is a great returner too, this shot could be key to the Serb challenging for Olympic gold.