The 56-year-old has signed a one-and-a-half year deal at Molineux and will be tasked with saving the club’s Premier League status.
Wolves sit 19th in the table, five points adrift of safety and Pereira’s first match in charge is a clash with fellow strugglers Leicester City on Sunday.
The Portuguese boss, who has replaced the axed Gary O’Neil in the dugout, took training for the first time on Thursday after completing his switch from Saudi Pro League club Al-Shabab.
Wolves are thought to have paid around £800,000 in compensation for his services.
Chairman Jeff Shi said: “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.”
The Wolves job is the 14th of Pereira’s two-decade coaching career but his first in one of Europe’s big five leagues.
He previously won two titles with Porto in his native Portugal and also claimed championships with Olympiacos and Shanghai SIPG.
Wolves sporting director Matt Hobbs confirmed he would be working with the new head coach to identify transfer targets ahead of the January window.
He added: “Vitor is a highly experienced and accomplished head coach who has demonstrated his ability to succeed at the highest level. His personality, desire and leadership qualities stood out to us during this process, and we’re excited to see how he applies his expertise here at Wolves.
“I’m looking forward to working closely with Vitor and his team on a daily basis, supporting them in every way possible - from getting the maximum out of our staff at Compton, to recruitment in the upcoming transfer window - as we work together to strengthen the squad and achieve our collective goals.”