Michael South hit a double-decker Coastliner bus on the A64 at Flaxton, near York, at 20:30 BST on Friday.
He was pronounced dead at the scene. Five bus passengers were hurt and the driver suffered serious leg injuries.
Tributes have been paid to Mr South, who was described as a "role model" to youngsters at Huby Cricket Club, where he was a member.
Club secretary Ken Piercey told BBC Radio York: "He joined as a teenager and enjoyed it. He was a good club man, he was a good role model for the young teenagers.
"It's a blow to the club and we are going to miss him."
Police said nobody else was in the ambulance and it did not belong to the NHS.
A Toyota Yaris was also involved in the three-vehicle crash, with one person in the car taken to hospital.
A man who died after crashing into a bus while driving a stolen private ambulance has been named.