Nelson Semedo wants to help Wolves back into Europe after joining from Barcelona and targeting a top six spot.
Last season's Europa League quarter-finalists missed out on the competition again this term after coming seventh.
But they have already broken their transfer record to buy Fabio Silva from Porto for £35million.
Now they have paid an initial £27.6m and potentially a further £9.2m in add-ons for Portuguese international right-back Semedo.
The ex-Benfica star, 26, has 10 major honours after three seasons at the Nou Camp and replaces Matt Doherty who quit for Spurs.
“I chose Wolves because it’s a very good team,” said Semedo after penning a deal until 2023 with an option to 2025.
“The team did very good things the last three years.
“I’m ambitious and I hope this year we can do very good things, reach the top six and, if it’s possible, do something special.
“Last year they did a very good season and it’s a very important team in England, in also Europe.
“To play in the Premier League is a dream from me.”
Semedo played 42 times for Barcelona last season, providing six assists and scoring on the last day of the season.
He could make his debut in the Premier League against West Ham on Sunday.
The defender has 13 caps alongside various Wolves compatriots like Rui Patricio, Ruben Neves and Joao Moutinho under Wanderers' Portuguese coach Nuno Espirito Santo.
Semedo added: “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.
“Nuno is a very good coach as well.
“He did very good things here in Wolves, and in other teams too. For sure I’m going to learn a lot from him.”
Wolves chairman Jeff Shi added: “It’s isn’t often that we have the opportunity to sign a world-class player from a world-class club.”
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