About 6.20am Monday, 8 May, emergency services were called to Lismore Road, Clunes, following reports of a two-vehicle crash.
At the scene, police from Tweed Byron and Richmond Police Districts were told that an SUV and van collided on a bend.
The driver of the SUV, a 43-year-old man, was stabilised by NSW Ambulance paramedics before being taken to Lismore Base Hospital in a critical condition.
The driver of the van, a 38-year-old woman, was taken to Lismore Base Hospital in a stable condition
Locals have reported that the road was closed for approximately eight hours.
Investigators have commenced inquiries into circumstances surrounding the crash, and urge anyone with information to contact Crime Stoppers on 1800 333 000.