The accident occurred just prior to 8am two kilometres south of Blayney on the Mid Western Highway, where it appeared a station wagon hit black ice, sliding off the road and hitting a tree.

Police blame ice for the accident.

Mr Ernie Muggleton and Ms Megan Riches both died at the scene, Ms Ritches instantly and Mr Muggleton, soon after with severe head injuries.

"We're just devastated," said Lois Camp, Canowindra's Royal Hotel licensee about the accident shock.

"Ernie was so careful a driver, always driving at 90 kilometres an hour. In fact, a good friend of his used to chip him and say Ernie, you are allowed to go a little faster.

"He would be the last person you would expect to be killed in an accident. It's tragic, he just had his 60th birthday on Friday and now he's dead.

"Megan, well she was only 19. She hadn't been here very long and she hadn't had the easiest life but she was trying to make a go of it."

A 46 year old Cowra woman, Debra May Maher died in a second accident which occurred almost simultaneously on the other side of Blayney near King's Plains.

The male driver, 43-year-old Neil Wylie of Cowra, is still in a serious, but stable condition at Royal Prince Alfred Hospital in Sydney, after emergency surgery on Saturday night.

The second accident involved a vehicle and trailer parked on the side of the road being clipped by a north bound B Double truck.

Both vehicles were forced from the road, with the female passenger, Debra Maher, killed instantly.

The Bathurst based Accident Investigation Unit is handling the second accident. At this stage, road conditions are not believed to be a factor.