Di Maria has made 136 appearances for world champions Argentina since his debut in 2008, playing in four World Cups and scoring in the 2022 final win over France.
He will take part in his sixth Copa America at the June 20th - July 14th tournament in the United States, where Argentina will bid to successfully defend their continental title.
"The Copa America will be the last time I wear the Argentina shirt," Di Maria wrote on his Instagram account.
"With all the pain in my soul and feeling a lump in my throat, I say goodbye to the most beautiful thing that happened to me in my career.
"I can't express in words how much the cheering of the fans has filled my soul in this last match, I enjoyed every second of with my team mates and friends," he added, referring to his last World Cup qualifier in which Argentina beat Brazil.
Di Maria rejoined Portuguese champions Benfica this year, the club he played for between 2007 and 2010 when he first arrived in Europe.
The winger also played for Real Madrid, Paris St Germain, Juventus and Manchester United.
