A woman who died in a crash on Appin Road, north-west of Wollongong, on Monday night has been named as popular high school teacher Melissa Bond.

The 25-year-old was commuting from John Therry Catholic High School in Campbelltown, where she worked, to her home in Thirroul.

Director of Catholic education in the Wollongong diocese, Peter Turner, confirmed Ms Bond died when her car and a truck collided head-on.

Mr Turner described her as a "fine young woman and a wonderful, passionate teacher".

Appin Road has been dubbed "the most dangerous road in Sydney" and has been the scene of more than 40 fatalities over the past 20 years.

New South Wales Roads Minister Duncan Gay has extended his condolences to "each and every family and friend that has lost a loved one" on the road.

Mr Gay said he was looking to see what more could be done to improve safety.

"Since 2011 the NSW Government has spent more than $8 million on Appin Road safety upgrades, and has committed a further $1.8 million to resurfacing work between Kellerman Drive and Brian Road, due to be completed by the end of June," he said.

"Sadly, the key killers on Appin Road are speed and fatigue, and no matter how much work we do, unless people take personal responsibility, I'm concerned we could see more tragedies occur."

But Opposition treasury and Illawarra spokesman Ryan Park said additional work needed to be done.

"What we urgently need to see is the type of infrastructure and road safety improvements that occurred at Picton Road under the Labor and Liberal governments some years ago," he said.

"That is, separation in the road, making sure the road surface is enhanced, and making sure that the shoulder, or side of the road, is a lot wider."