A motorcyclist aged in his 20s died after colliding with a Mazda sedan on Barkers Lodge Road at Picton, near Camden about 2.45pm on Sunday.
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The motorcyclist died at the scene but the male driver of the Mazda was uninjured.
Police from Camden Local Area Command established a crime scene and are investigating the circumstances surrounding the crash.
While north west of Sydney, three men died when the Mitsubishi SUV they were travelling in collided with a Subaru sedan on the Bells Line of Road at Kurmond, near Richmond, just after 3.30pm.
NSW Police said the three men, aged in their 20s, died at the scene and have yet to be formally identified.
Transport for NSW statistics show 229 people died on the state's roads between January 1 and August 27 this year, up from 205 for the same period in 2014.
January was the worst month, with 37 fatalities, followed by May when 36 people lost their lives on the road.
