The sad incident happened in KwaZulu-Natal on Monday morning.
He was thrown from the vehicle and died on the scene whereas his female companion is in a critical condition in hospital.
Ngcongca was recently released by Mamelodi Sundowns to play for AmaZulu FC in the 2020/2021 season.
Ngcongca previously played for KRC Genk in Belgium and ES Troyes AC in France.
The 33-year-old made 53 appearances for the Bafana Bafana including Africa Cup of Nations and the 2010 FIFA World Cup