It happened on the Killarney to Tralee road about 11 kilometres outside Killarney last night.
The woman, who was the only person in the car, was taken to Kerry General Hospital with serious injuries.
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The driver of the Garda van suffered minor injuries.
The Garda Ombudsman is investigating and anyone with information is asked to contact Killarney Garda Station on 064 6671160.
