Police from the Metropolitan Crash Investigation Unit issued a statement this morning (Wednesday) saying they had charged a Picton man, 67, with negligent driving occasioning death.

The man was charged last night when he attended Camden Police Station. He will appear at Picton Local Court on January 27.

Five people - a man aged in his 40s, two females aged in their 40s, a 23-year-old woman, and a three-month-old child, all who had fled Afghanistan to settle in Australia - were killed in the head-on crash between a semi-trailer and a Toyota Camry about 8.15am.

A Wilton man, 56, who was driving the semi-trailer, was taken to Campbelltown Hospital suffering shock.

The Picton man who has been charged is alleged to be the driver of a separate vehicle.