The 56-year-old Portuguese manager has left Saudi Pro League club Al Shabab to join Wolves on an 18-month contract after the Midlands side, battling to avoid relegation, sacked Gary O'Neil.
The widely travelled Pereira was close to replacing Rafael Benitez as Everton manager in 2022.
During an extensive managerial career, Pereira has won two Primeira Liga titles with Porto and the Greek Super League with Olympiakos.
The BBC reported Tuesday that Wolves would pay around one million euros ($1 million) to bring Pereira to the English top flight.
Wolves chairman Jeff Shi said Thursday: "We are delighted to welcome Vitor Pereira to Wolves as the new head coach of our men's first-team. Vitor is a highly respected and experienced coach who has achieved success across different leagues and will bring a new approach for the test ahead.
"This is a challenging moment for the club, and we want to thank Vitor for taking on this responsibility. We have full confidence in his ability to guide us back on track, alongside the players and staff, and the entire club will be united in supporting him to achieve success."
Wolves, second bottom in the Premier League, said Pereira took his first training session with the club on Thursday and would be in charge for their match away to fellow relegation candidates Leicester -- five points above them in the standings -- on Sunday.
O'Neil was sacked after Saturday's 2-1 loss at home to Ipswich, the club's fourth defeat in a row, left Wolves with just nine points from 16 league games.
O'Neil was appointed in August 2023 following the departure of Julen Lopetegui and signed a new four-year deal with the club in August this year.