According to BBC, Murray, a two-time singles champion at SW19, will compete in both the men’s and mixed doubles less than a month after returning following hip surgery.
American Williams, a 23-time Grand Slam singles winner, had earlier told journalists: “If you guys really want it… all right, done.”
The pair are expected to play their first match together on Thursday.
Murray, who won Queen’s with Feliciano Lopez, will partner Frenchman Pierre-Hugues Herbert in the men’s doubles.
The Scot was turned down by world number one Ashleigh Barty before suggesting he might pair up with 37-year-old Williams, who has won seven doubles titles at Wimbledon.
Murray said: “Serena is obviously a brilliant player, has a great doubles record and is brilliant on grass obviously. She’s arguably the best player ever.”
Laughing, he added: “So she’d be a solid partner.”
The only issue will be whether the American’s knees will cope with the extra demands of playing doubles as well as singles – and whether Murray’s fitness holds up to what will be a packed doubles programme if they have a good run.
Williams has struggled with a knee injury this year but beat Giulia Gatto-Monticone on Tuesday.
Murray played mixed doubles at Wimbledon in 2006 where he teamed up with Belgium’s Kirsten Flipkens and reached the second round.
He was also a silver medallist with Laura Robson in the London 2012 Olympics which were played at the All England Club.
Williams is a two-time mixed doubles Grand Slam champion, having partnered Max Mirnyi to win Wimbledon and the US Open in 1998.
Some 64 pairings compete in the mixed doubles, which is played over the best of three sets.