A 33-year-old woman is dead after her bicycle and a car collided in Pymble in Sydney's north on Sunday morning, the fifth cyclist to die on NSW roads this year.

The woman was travelling within a small group of cyclists heading southbound on Mona Vale Road at the intersection with Woodlands avenue when the crash occurred.

A 37-year-old male driver of a Toyota Corolla sedan will undergo drug and alcohol testing.

"We are deeply saddened by the unnecessary death of a young woman (who we have connections with) this morning as she cycled with her bunch down Mona Vale road," the West Pymble cycling club Velo 2073 wrote on Facebook.