The 23-year-old defender moved to Molineux from relegated Hull for an undisclosed fee, signing a four-year contract with the option of a fifth year.
"I'm very excited and very happy," he said.
"It was important for me to try and stay in the Premier League because I enjoyed last season even though it was disappointing that Hull were relegated.
"I'm delighted to be staying in the league and even more so at a club with such history like Wolves."
The Frenchman, who will join up with the squad for pre-season training in two weeks' time, believes he can enhance his reputation playing under Mick McCarthy, the former Republic of Ireland defender and manager.
"As soon as I know Wolves were interested it was always going to be a move which really appealed to me," added Mouyokolo.
"I've heard a lot of good things about Mick McCarthy and have enjoyed talking to him and am looking forward to working with him and improving my game."
Mouyokolo is Wolves' third signing of the summer, following Jelle Van Damme and Steven Fletcher to Molineux, while Adlene Guedioura's loan move from RSC Charleroi has become a permanent deal.
Mouyokolo began his career with LB Chateauroux in French Ligue 2 albeit without making a senior appearance for them.
He impressed for FC Gueugnon before moving to Boulogne, where he made his name.
In January 2009, Mouyokolo agreed a move to Hull but stayed on and helped Boulogne to promotion to Ligue 1.
Rather than featuring for Boulogne in the French top flight, he switched to the KC Stadium, making 23 appearances and scoring one goal - in the 1-1 draw with Chelsea - but could not prevent the Tigers from being relegated to the npower Championship.