The Premier League club have announced the 26-year-old has signed a three-year deal at Molineux with an option to extend until 2025.
Semedo, who was earned 13 caps for Portugal, joins Wolves after three seasons at the Nou Camp.
Semedo told the club’s website: “I chose Wolves because it’s a very good team that plays very good football. Last year they did a very good season and it’s a very important team in England, in also Europe. I hope this year we can do very good things.”
Semedo is looking forward to linking up with his fellow Portuguese Nuno Espirito Santo, the Wolves coach.
He said: “Coach Nuno is a very good coach. He did very good things here in Wolves, and in other teams too. For sure I’m going to learn a lot from him.”
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The move will also unite Semedo with a number of international team-mates.
He said: “I talked with some of them and they told me very good things about the club, about the team. I hope I can help them to succeed too.”
Wolves executive chairman Jeff Shi believes the signing is a coup for the club.
He said: “It’s isn’t often that we have the opportunity to sign a world-class player from a world-class club.
“Nelson’s signing shows we will never stop progressing and we are still hungry and humble in our heart.”