Bowral police say the man was driving south on the northbound side of the Hume Highway at Bargo when his Nissan utility was involved in a head-on collision with a northbound car at around 6.45pm.

Another eight vehicles became entangled in the collision, which resulted in four people being taken to various hospitals to have minor injuries treated.

The man underwent a roadside breath test, which returned a positive reading, and he was taken to Camden police station for a breath analysis.

He was charged with high-range drink driving after he recorded a PCA (prescribed concentration of alcohol) 0f 0.225.

The man's licence was suspended and he was conditionally bailed to appear in Picton Local Court on October 25.

Meanwhile, police are investigating a possible abduction after a woman was hit by a car on the Hume Highway on Monday night.

The woman, believed to be middle-aged, was knocked down by the car on the Hume Highway at Pheasants Nest early Monday night, and has since turned up in a hospital in Victoria.

Police were unable to confirm where the woman was from and how she ended up across the border after the accident, and said their enquiries were continuing.