In an interview with Argentinian channel TyC Sports, the 136-cap international said he won't be taking part despite the potential opportunity to be involved in another Olympic campaign with Lionel Messi. The pair helped Argentina to gold at Beijing 2008, along with current coach Javier Mascherano.
Mascherano's side need to qualify through the South American pre-Olympic tournament currently being held in Venezuela which ends on 11 February.
"It's not possible, I've already made the decision to finish the Copa America," Di Maria said.
"I've gained the power to decide so far and the Copa America will be the last one, also because I've been suffering for many years in the national team, with a lot of injuries and things not working out for me.
"It was a tough time for me, but from the Copa America we won, everything was different - joy and happiness. Being able to enjoy being in the national team 100 per cent was something I deserved, that's why I've kept going and I want to keep going a bit longer, but the end is at the Copa America."
The 35-year-old said this is the "perfect time" to say goodbye to the national team, given the promising generation coming through and currently playing in the pre-Olympic tournament.
"I think it will be the perfect moment to say goodbye to this shirt, it will certainly hurt, but there are a lot of kids coming up," he said.
"It was the same for me when I arrived, there were a lot of older players who kept going for a long time and for a while that didn't go down well.
"Now it's time to take a step forward, it's fine that we're world champions, but there are times when we have to take a step back and make room for the new generation coming through, which is very good."
