He was treated at the scene before being taken to Royal Prince Alfred Hospital in a critical condition, but died a short time later, Sydney media reported.
Reports on social media confirmed the deceased was Holoua Tonga, a Tongan player at Balmain Rugby Club.
An emotional message was posted to the club’s Facebook page this morning said:
“We are sorry to pass on the news that Holoua Tonga passed away this morning after a motorcycle accident on the way to work.
Holoau seen here from Saturday’s Kentwell win was a hardworking family man with a beautiful wife & young family. He will be sadly missed by all that knew him”.
The driver of the car, a 50-year-old man, was uninjured.
He was taken to Sydney Hospital for mandatory blood and urine testing.
Officers from Redfern Local Area Command are investigating.
Police have asked any witnesses to call Crime Stoppers on 1800 333 000.
A report will be prepared for the coroner.