Serena Williams, looking to retain her women's title and match Steffi Graf's professional era record of 22 major singles crowns, opens up against a qualifier.
Djokovic, seeded number one, could face a semi-final with third seed Roger Federer, the seven-times champion he beat in the last two finals at the All England Club.
The 29-year-old, the first man to win the year's first two grand slams since Jim Courier in 1992, is bidding to become the first man to sweep all four majors in the same season since Australian great Rod Laver in 1969.
He could face a tricky path though with big-serving Canadian Milos Raonic, seeded six, looming in the quarter-finals.
Federer, who missed the French Open through injury after contesting 65 consecutive majors, plays Argentina's Guido Pella in the first round.
Second seed Andy Murray faces an all-British first round against wildcard Liam Broady.
Fourth seed Stan Wawrinka, Murray's prospective semi-final opponent, begins against American teenager Taylor Fritz.
American veteran Williams, stuck on 21 grand slam singles titles since beating Spain's Garbine Muguruza in last year's final, could face Italian Roberta Vinci in the last eight.
Vinci ended her dream of winning the calendar year slam at last year's U.S. Open.
Second seed Muguruza, fresh from winning the French Open, faces Italy's Camila Giorgi in round one.
(Reporting by Martyn Herman; editing by Sudipto Ganguly)
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