Serena Williams has already shown glimpses of her best form at Wimbledon and will be hoping to extend her run with victory over Kristina Mladenovic in the third round on Friday.
The seven-time champion, 36, who returned in February after giving birth, is second on Centre Court.
Eight-time winner Roger Federer, 36, plays German Jan-Lennard Struff last on Centre in round three.
Five-time winner Venus Williams opens on Court One against Kiki Bertens.
2016 runner-up Milos Raonic, seeded 13, faces 24-year-old Austrian Dennis Novak, who has never progressed past the third round of a Grand Slam.
American 10th seed Madison Keys, the 2017 US Open runner-up who also reached the semi-finals at this year’s French Open, will be favourite to overcome world number 120 and qualifier Evgeniya Rodina, who has won five matches en route to this stage.
If Keys wins it could set up an all-American last-16 encounter against Serena Williams.
Sixteen of the 32 men’s seeds have been knocked out in the opening two rounds, along with 14 in the women’s draw.