Two of four victims of an horrific crash on a Victorian freeway, who had just stopped for a coffee when they turned into an oncoming truck, have been identified.

Two married couples, aged in their 70s, were killed when the car they were travelling in collided with a truck at the intersection of the Hume Freeway and Wenkes Rd at Chiltern, just before 10.30am on Thursday.

Trevor and Lorraine Breen of Wagga Wagga were one of the couples killed, 7 News reported on Friday.

Victorian Assistant Commissioner for Road Policing Glenn Weir told reporters on Friday the group had stopped in the Victorian border town “for a break and a coffee” before they turned back onto the freeway.

It is understood the yet to be identified couple were also from central NSW and were also on their way to Melbourne to visit family and friends.

“A catastrophic collision occurred and four people have been killed instantly,” Mr Weir said.

The 30-year-old truck driver has been interviewed by police in hospital and mandatory testing found he was not affected by drugs or alcohol.

“You can imagine the shock that he’s in, he went to work and was just driving his truck and he’s been confronted without something beyond his control that has resulted in him being involved in such a tragic incident,” Mr Weir said.

He said there were a number of witnesses who saw the collision described it as a “confronting scene”.

“Seeing the vision from the scene, even for me, it’s quite confronting … there were a number of people who witnessed the collision,” Mr Weir said.

“Nothing will save you from a collision at that speed.”

Over the past 10 years, there have been 10 collisions at that intersection and this is the first fatality.

Mr Weir took the opportunity to urge motorists to take more care and pay attention on roads.

“It is another tragic reminder of how what appears to be a moments inattention can lead to such catastrophic outcomes,” Mr Weir said.

“You can travel 300km and do the right thing for 299.9 kilometres but one mistake is unforgiving, the roads are unforgiving.”

Major Collision Investigation Units are investigating the incident.