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.