A man has died and two other people have been hospitalised after a two-car crash in south-western Sydney.

The 25-year-old driver died after his Ford Falcon collided with a Toyota Rav4 on the Hume Highway in Campbelltown about 11.30pm on Saturday.

His passenger, a 26-year-old man, was taken to Liverpool Hospital in a stable condition with suspected internal injuries.

A 27-year-old woman, the driver of the Toyota, suffered a suspected fractured arm and was also taken to Liverpool Hospital for treatment and mandatory testing.