The three-day event will feature various celebrities in discussion with either one another or reporters, as well as cocktail recipes and musical performances.
Jordan will launch the festivities with Williams on April 13, when Gal Gadot and Andra Day will also take part in separate chats with Vanity Fair correspondents, and "Transparent" stars Kathryn Hahn and Judith Light will catch up online.
Laura Dern will top the second night of events in an interview with Vanity Fair's editor-in-chief Radhika Jones, while "Judas and the Black Messiah" director Shaka King will touch base with comedian Ziwe, and Glenn Close will host a costume retrospective with designer Ann Roth and collaborator James Nadeaux.
There will also be a game night segment featuring Jessica Alba, Eva Longoria, Kelly Rowland, and "The Crown" actress Emma Corrin, before Amanda Seyfried and Julianne Moore headline the fun on April 15.
Paris Hilton, Sacha Baron Cohen, and director Jon M. Chu are all on the bill for the final night of "Cocktail Hour Live!", as are Haim and Maya Rudolph, who will face off in a game of trivia against Andy Samberg and his The Lonely Island bandmates.
Each night of programming will begin at 7pm ET. For tickets and more information, visit Vanity Fair's "Cocktail Hour Live!" official page.
A portion of proceeds will benefit the Motion Picture & Television Fund to help support COVID-19 relief efforts.