The southbound car collided with a Pantech truck travelling in the opposite direction on the New England Highway between Guyra and Glen Innes about 6.15 (AEST) last night.
Three people travelling in the car died at the scene.
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Police say a fourth car passenger was taken to Armidale Hospital, but died shortly afterwards.
The New England Highway is closed in both directions, just south of Inn Road near the Ben Lomond Range.
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