Munetsi, a Zimbabwe international, moves to Molineux in a permanent transfer.
The midfielder has signed a contract to 2028.
Now 28, Munetsi spent the early part of his career in South Africa, representing Ubuntu Cape Verde, Baroka and Orlando Pirates.
Chairman Jeff Shi said: “Our staff travelled to France to ensure this deal was done on deadline day, as it was important for the club, and we’re pleased to bring an experienced player into the group at an important time of the season.
“We’re excited to have Marshall on board, and I hope he can help us achieve our aims. He’ll have the full support of all of us at Compton Park and I hope he will have a long and successful time as part of the Wolves family.”
Sporting director Matt Hobbs said: “It was important for us that Vitor has a number of options in each position and Marshall is a well-rounded midfielder who is physically up for the challenge of the Premier League.
“Marshall’s played with Agba, who has settled quickly into the group, and now he’ll have the support of everyone here at the club. He’ll be another option for Vitor and we’re looking forward to having him as part of the club.”