Semedo is not in the plans of new coach Ronald Koeman and did not feature in the Gamper Trophy game against Elche at Camp Nou on Saturday.
The 26-year-old has been identified by Wolves manager Nuno Espirito Santo as a replacement for Matt Doherty, who joined Tottenham earlier this summer, and is expected to join the large Portuguese contingent at Molineux.
Capped 13 times by Portugal, Semedo has spent three seasons at Barcelona and has made 124 appearances for the Catalan club since a move from Benfica in 2017.
Semedo's sale will bring in important funds for Barcelona, with the club needing to raise money before new players can be brought in this window.
That could include a new right-back as well, with only Sergi Roberto left to occupy that position once Semedo leaves, after Moussa Wague was loaned to Greek side PAOK on Monday.