Pauline Smith was driving a blue car which collided with a white Holden Vectra on the Western Highway in Great Western near the Grampians before 8am today.
She was pronounced dead at the scene.
The second driver was taken to hospital with non-life-threatening injuries.
He assists the police in their investigation.
Ambulance Victoria Acting CEO Libby Murphy released a statement tonight to mourn Smith’s death.
“We stand united in shock and sadness as an organization today following the sudden passing of our paramedic colleague Pauline Smith,” Murphy said.
“Our deepest condolences go out to Pauline’s husband, Stephen, and her three children, family, friends and close colleagues.
“Pauline was a much loved and respected member of the Grampians community and she will be sorely missed.”
Police are calling on anyone who saw the Holden before the accident to contact them.
Part of the highway is expected to be closed for the rest of the day.
Drivers are encouraged to take alternate routes.