The 31-year-old, who made nine appearances for his national team, was travelling with four passengers when he was involved in the incident and subsequently passed away in the early hours of the morning.
Henyekane was on loan at Premier Soccer League club Free State, with Stars confirming the news on their official website.
"Free State Stars hereby expresses its heartfelt condolences on the passing away of star striker Richard Henyekane in the early hours of this morning," read a statement.
"Henyekane was travelling with four other passengers when they were involved in a tragic motor vehicle accident.
"We wish to say to the Henyekane family that they must know that we are with them at all times, and trust that they will put all their sorrows in the hands of God the Almighty in this hard period.
"To the Stars family of fans, sponsors, supporters and others we believe that this is a period in which you will remain steadfast in praying for Henyekane's team-mates as they come to terms with this sad moment.
"South African football has lost yet another one of our promising players... go well 'Kimberley Express'."
