Defending champion Djokovic opens play on Centre Court against Germany’s Philipp Kohlschreiber at 13:00 BST.
Williams, who is half way to a possible calendar Grand Slam, plays Russia’s Margarita Gasparyan on Court One.
Fourth seed Maria Sharapova takes on Johanna Konta, one of four Britons in action on day one, in the second match on Centre Court.
Konta will be making her debut on the main show court, to be followed by French Open champion Stan Wawrinka against Portugal’s Joao Sousa.
British number one Heather Watson plays French 32nd seed Caroline Garcia last on Court Two.
Play on the outside courts gets under way at 11:30 BST, with wildcard Liam Broady taking on Australian Marinko Matosevic first on court 18 and the Briton’s sister, Naomi Broady, up against Colombian Mariana Duque-Marino later in the day.
Andy Murray, Laura Robson, Roger Federer, Rafael Nadal and Petra Kvitova will be among those in action on Tuesday, when temperatures are expected to push 30C as hot weather is forecast for the opening days.
A record prize fund of £26.75m is on offer at the 129th Championships, with the men’s and women’s singles champions each receiving £1.88m and first-round losers collecting £29,000.
Almost half a million spectators will pass through the gates of the All England Club over the 13 days of action, with upwards of 140,000 portions of strawberries eaten.
Credit: BBC.com
