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.
