The collision occurred shortly before 4:30 a.m. just north of Point Mugu Rock, according to the California Highway Patrol.
It appears one of the vehicles crossed the center lines into oncoming traffic and struck the other head-on.
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Officers and firefighters arrived to find both vehicles engulfed in flames.
Five people were pronounced dead at the scene, a CHP spokesperson said. They were not immediately identified.
The dead included a male driver who was alone in the car and four people who were in the SUV.
PCH was closed in both directions as an investigation got underway.
The lanes were reopened just before 4 p.m., Caltrans said.
Drivers were urged to use the 101 Freeway as an alternative route.
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The cause of the crash is unknown.
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