Moutinho knows the marquee signing from Barcelona very well, having played with the 26-year-old for Portugal.
Right-wing-back Semedo has come in for an initial £25.7million which is due to quickly rise to £29m and could even increase significantly further in various add-ons over the years.
And Moutinho believes he has all the right tools to be a big success at Molineux, as he said: “I know him very well.
“I saw him play in Benfica, Barcelona and the national team.
“He’s a great player and a great person, too. This is important for us because our group is very good.
“For these three years, it’s been one of the best groups I’ve had in football.
“To bring players like that, with these qualities, it’s very good for us. I think he is going to help us a lot in the game.
“That’s what we expect. Of course, he will expect to do the best to help the team.”
Semedo signed a deal until the summer of 2023 – the club having the option to extend his contract until the summer of 2025 – having made more than 100 appearances for Barcelona while gaining 13 Portugal caps.
He joins an already vast Portuguese contingent at Wolves including teenager Fabio Silva, who was snapped up for a club-record £35m earlier this summer.
On Silva, Moutinho said: “He has great potential. He’s a young guy who needs to continue to work, to show the qualities he has.
“I think he has everything to show how good he is, and we will try to help him improve and learn every day with us – and with Raul Jimenez as they play the same position.
“It’s important because young players come and like to learn. I think it’s great to have him.”
While those two have come in along with Fernando Marcal, Vitinha and Ki-Jana Hoever, Diogo Jota has left for Premier League champions Liverpool.
Moutinho wished him well on Merseyside, too, as he said: “I’m very happy for him as he’s a very good player. All the people know, and he’s a great person.
“He’s the kind of player every coach likes to have. Jota, I hope, will do a great career.
“He has already done a lot of things but now he can improve and win more things. He has all the qualities to do it.”
Amidst all of that though for Wolves, who travel to West Ham on Sunday, perhaps the biggest signing of the summer was boss Nuno Espirito Santo penning a new three-year contract.
Moutinho added: “What he, the team and the staff have done for three years is amazing.
“They’ve done a great job and to continue with the same coach and staff, we already know what he wants.
“We continue to work to get better. It’s difficult as the Premier League is the best league in the world, but we have ambitions and we want to continue every year to do our best.”