The actors, who starred together in "Driving Miss Daisy" in the West End and on Broadway, will be directed by Mark Rylance in a production of the comedy slated to open in September.
It will offer a distinctive take on the couple, usually presented as young-ish lovers -- Redgrave is 75 and Jones 81.
Old Vic artistic director Kevin Spacey -- the Oscar-winning actor -- said the casting of "two of the greatest legends ever to grace the stage" would show Shakespeare's comedy in a new light.
"It is no longer about two people who are starting their lives out saying, 'I'm not going to have anything to do with this love business,'" he said. "It's two people who have lived their lives this way.
"That's the great thing about Shakespeare -- nobody owns these parts. We just borrow them for a short time. Every actor brings to a role something different, something unique."
Jones made his Broadway debut in 1957 and has had distinguished stage and screen careers, though he is best known to millions as the voice of "Star Wars" villain Darth Vader.
Redgrave, a member of a British acting dynasty, has been nominated for six Academy Awards and won one, for her supporting role as an anti-Nazi activist in 1977's "Julia."
"Much Ado" is part of a 2013 season that includes a production of Tennessee Williams' "Sweet Bird of Youth" starring "Sex and the City" actress Kim Cattrall as a fading Hollywood star.
Spacey predicted: "She is absolutely going to set the stage on fire."
And he said that, as an American "I'm almost ashamed I haven't produced Williams since I started" at the Old Vic.
The lineup also includes a revival of Terence Rattigan's drama "The Winslow Boy" directed by Lindsay Posner and a British tour of the Old Vic's acclaimed production of Michael Frayn's farce "Noises Off."
Spacey said the lineup reflected the fact that "the Old Vic has always been first and foremost an actors' theater, a home for great talent and memorable performances."
Spacey, who won Academy Awards for "The Usual Suspects" and "American Beauty," has led the Old Vic since 2003.
He has been credited with restoring the fortunes of the 200-year-old venue, which has provided a stage to performers including John Gielgud, Peggy Ashcroft, Alec Guinness, Peter O'Toole, Judi Dench and Maggie Smith.
He has starred in several of its productions, including an acclaimed "Richard III" last year, and has won praise for drawing both broader audiences and stable funding to the venue after years of uncertainty.
Spacey said he would step down in 2015, having helped establish the Old Vic "as a destination theater again."
"I think a theater needs new blood," he said. "I am excited about the transition."