The 50-year-old woman and a 51-year-old man were travelling on a motorcycle along the Great Western Highway towards Bathurst, near Diamond Swamp Road, when the crash occurred at 10.30am.

Emergency services were called to the accident site, located 35 kilometres from Bathurst, however, the woman died at the scene.

The man was treated by paramedics before being flown to Liverpool Hospital in a critical condition.

A NSW Ambulance spokesman said the man had head, chest and leg injuries.

Both people involved in the accident were from Sydney.

Officers from Chifley Local Area Command established a crime scene and will investigate the circumstances surrounding the crash.

Duty Officer Inspector Gerard Powell said on Sunday that police were yet to speak to the man involved in the accident about its possible cause.

The highway was closed until just after 3pm.

Saturday’s spate of road accidents across the state also left a number of people with serious injuries.

NSW Police Traffic and Highway Patrol Command officers have urged people to take care on the road after the crashes in Bathurst, Port Botany and Wee Waa, as well as two separate, serious motorcycle crashes on the Oxley Highway, 80 kilometres west of Port Macquarie.