Semedo joined the La Liga giants from Benfica ahead of the 2017-2018 season.
The 26-year-old could not become an automatic starter during his time at Camp Nou, as he jostled for a starting berth at the right-back spot with Barcelona academy graduate Sergi Roberto.
Wolves have agreed to sign Semedo for a fee in the region of £30million as they look to replace Matt Doherty, who ended his decade-long stay at Molineux by joining Premier League rivals Tottenham Hotspur earlier this month.
Semedo took to his Instagram account to announce his Barcelona exit by sending an emotional message to the club.
“Thank you very much Barcelona for giving me the opportunity to live the dream of wearing this shirt, of playing in Camp Nou, of learning and enjoying the best in the world,” he wrote.
"Thank you for making me grow as a player and as a person. They were three wonderful years that I will never forget.
“Thank my colleagues, staff, fans and all the people who helped me since I arrived until today. I wish you the best luck in the world.”
Semedo played 124 times for the Blaugrana, winning four trophies which include two La Liga titles in his three-year stay.