The woman, who was the passenger, was airlifted by helicopter at the crash site to the Royal Melbourne with significant injuries to her legs.
The driver was initially transferred to Deniliquin Hospital with head injuries and fractures before being taken to Melbourne.
Murray River Police District Detective Inspector Jy Brown said police investigations are still continuing, with the cause of the crash still unknown.
He did say speed and alcohol are being investigated as factors.
‘‘It was at about 3.45pm the Hilux was being driven east on the Wakool Road by the male, aged 26,’’ Det Insp Brown said.
‘‘When the ute was about 40km west of Deniliquin the driver, for unknown reasons, left the roadway.
‘‘After swerving right, he appears to have lost control and the car is believed to have rolled at least seven times. The car came to a stop about 100m from where the car left the road.
‘‘Investigations continued well into the night, and we are now waiting to speak with the driver and his passenger, aged 22.’’
Deniliquin Volunteer Rescue Association Captain Chris Holloway said his team was tasked with stabilising the vehicle before using hydraulic cutting equipment to gain access to the driver and passenger.
‘‘We then assisted New South Wales Ambulance in extracting the driver before working on the passenger,’’ he said.
In addition to police, paramedics and VRA members, NSW Rural Fire Service crews responded to the incident.
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