The 36-year-old former Barcelona defender refused to commit to a new deal with PSG and will move on as a free agent.
Alves has been linked with a move to the Premier League and last month stated that he has "a lot of options".
The veteran revealed he will be leaving the French capital after scoring in Brazil's 5-0 Copa America thumping of Peru on Sunday (AEST).
Alves posted on Instagram: "Today I close another cycle in my life, a cycle of victory, learning and experiences.
"I would like to thank the PSG family for the opportunity to together build a page in the history of this club.
"I would like to thank all the staff for their affection, respect and complicity from day one ... you make this club a little more special.
"It was two years of resilience and continuous reinventing to fulfil my mission, but in life everything has a beginning, a middle and an end and now the time has come to put that final point here.
"I apologise if at any point I was not up to the pitch, I apologise if at some point I made a mistake, I just tried to give my best."