The left-back had featured regularly for the Tykes this season, but he has insisted that he couldn't turn down a move to Molineux.
The 25-year-old told the Express & Star: "There aren't too many opportunities to come to a club the size of this. The training ground is Premier League standard. The facilities at our disposal are incredible and it's a lovely place to come and work.
"I played for Barnsley when we lost 3-1 at Molineux last season so it's nice to have had a little a taste of what it's like at the ground.
"There was a great atmosphere on the night and it's an incredible stadium."
Golbourne becomes the third player to move to Wolves this season after Sam Ricketts and Kevin McDonald.