World number one Djokovic, who is bidding to take another step closer to the first calendar Grand Slam since 1969, has defeated Federer in the last two finals at the All England Club.
The draw means that second seed Andy Murray, the 2013 champion, was lined up for a semi-final against fourth seeded Stan Wawrinka.
Three-time champion Djokovic completed the career Grand Slam with victory at the French Open earlier this month and now holds all four majors. It was his 12th career major and made him the first man since Jim Courier in 1992 to win the Australian and French Opens in the same year.
The 29-year-old Serb begins his Wimbledon campaign against British wild card James Ward and could meet big-serving Canadian Milos Raonic in the last-eight.
Murray takes on compatriot Liam Broady in the first round with a potential clash against Australia’s Nick Kyrgios in the fourth round. Frenchman Richard Gasquet is a possible quarter-final rival.
Federer, seeded three but enduring an injury-hit season, starts against Argentina’s Guido Pella, ranked 51 in the world.
The 34-year-old Swiss, the holder of a record 17 majors, could face Japan’s Kei Nishikori in the quarter-finals. If seedings play out, Wawrinka would come up against in-form Dominic Thiem of Austria for a place in the last-four.
Defending women’s champion Serena Williams, chasing a seventh Wimbledon title to equal Steffi Graf’s Open era record of 22 majors, was drawn to face Polish third seed Agnieszka Radwanska in the last-four. Radwanska made the final in 2012.
French Open champion Garbine Muguruza, who beat Williams in the Roland Garros final but lost to the American in the Wimbledon championship match in 2015, could face Australian Open winner Angelique Kerber in the last-four. Spanish star Muguruza begins against Italy’s Camila Giorgi.
The women’s draw held out the tantalising prospect of an all-Williams final with sister Venus in the opposite half of the draw.
Venus, 36 and a five-time champion, is seeded to face Muguruza in the last-eight while Serena could come up against Italy’s Roberta Vinci who dumped her out of the US Open semi-finals in 2015.
In other potential quarter-finals, Radwanska could meet Belinda Bencic while Kerber was drawn to face Simona Halep.
Serena starts against a qualifier and will face either fellow American Christina McHale or Slovak veteran Daniela Hantuchova in the second round. Two-time champion Petra Kvitova meets Romania’s Sorana Cirstea in her opener.
British number one Johanna Konta, the first home seed in the women’s draw since 1984, takes on Monica Puig in the first round.