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A woman rock climber has suffered multiple serious injuries after plummeting down a 30-metre cliff in the Blue Mountains, west of Sydney.

The woman, aged in her 20s, is in a critical condition in hospital with injuries to her legs, chest, back and head.

She was believed to be rock climbing on Wednesday with a man in his 20s, who has suffered a serious leg injury.

"He is otherwise stable," said a spokesman for Ambulance NSW.