The 26-year-old is set to come in on a long-term deal, with the deal potentially involving add-ons, as Nuno Espirito Santo's first-choice right-wing-back.
Wolves have already signed youngster Ki-Jana Hoever for a fee which could rise to £13.5million from Liverpool, and now Semedo is set to follow suit to bolster that position even further.
Nuno spoke of his desire to sign somebody for the role on top of Hoever in his press conference on Saturday, as he said: “We need to fulfil the right-wing back position, of course.
“We look at our squad and see we still have gaps to fill. We have the target. We know what the squad needs and we want, as soon as possible, to finish our squad.
“We know the transfer market is still open and anything can happen, like I said before, and we have to react. We need to finish our squad.”
The right-wing-back position has been under the spotlight ever since Matt Doherty was sold to Tottenham.
But Semedo ticks a lot of boxes for Wolves as a Portuguese international at a good age and of top-level experience, while also a client of super-agent Jorge Mendes, who is thought to have been key in this deal.
Semedo has played 124 times for Barca, who are having to sell players to fund new signings, and gained 13 Portugal caps.
He was an unused substitute as Ronald Koeman’s side beat Elche 1-0 on Saturday.