Emergency services were called to the collision on Cape Otway Road, between Mount Duneed and Ervins roads in Moriac about 8.40pm.
Police believe both vehicles were travelling in opposite directions when one veered onto the wrong side of the road.
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A 23-year-old from Moriac and a 59-year-old from Winchelsea, died at the scene.
Geelong Highway Patrol are investigating the collision and will prepare a report for the Coroner.
