Di Maria spent four seasons at the Santiago Bernabeu, winning a La Liga crown and Champions League title among numerous other trophies.
Despite his history at Madrid, Di Maria, 29, said he would play for Barca if the opportunity presented itself.
"My relationship with Madrid is finished because my cycle there ended," he told So Foot .
"Frankly, I wouldn't have a problem to play at Barca, to the contrary."
While playing for Barcelona wouldn't be off limits for the Argentine, who turns 30 on Wednesday, he does still have some loyalty to one of his past clubs.
Di Maria played 35 times at senior level for boyhood club Rosario Central and claims he couldn't bring himself to turn his back on the team that raised him.
"The only club I couldn't play for is Newell's Old Boys because I am a fan of Rosario Central," he said.
Di Maria and PSG will face former club Madrid in the premier tie of the Champions League round of 16.
The first leg is set to take place Wednesday, with Di Maria having staked a strong claim for a starting spot with a hat-trick in a 4-1 smashing of Sochaux last Tuesday.