'Schillo' sent a message to Bafana coach Gordon Igesund and Safa CEO Robin Petersen late on Monday stating his intentions to quit the national team.
“It is with regret that I wish to inform you that I’m not available for the national team,” Pienaar wrote.
"I am proud to have represented and captained my country," he said in a statement. "There is a lot of very good young talent coming through and perhaps it is time for them to be given an opportunity.
"I wish the coaching staff and the players all the very best for the future."
Pienaar has served the nation for 10 years and Igesund says the nation must “respect” his decision to call it quits.
Greece-based defender Bongani Khumalo will now take over as captain.