Paul Dee, 63, died alongside Graham Bowen, 56, in the crash near Chop Gate on the B1257 on Sunday.
Mr Dee, from Redcar, worked as a police officer for 30 years before retiring from the force and taking up a new role as an ambulance driver.
His family have paid tribute to him.
In a statement, they said: “Our family are heartbroken at the tragic and untimely loss of a loving husband, father, stepfather, father-in-law, grandad and brother.
“Paul was a dedicated police officer for 30 years and an ambulance driver for four years after retiring from the police.
“He was even more dedicated to his family and large circle of friends.
“We all love and miss him every minute. Taken too soon and sadly missed.”
The Chief Constable of Cleveland Police, where Mr Dee had worked, also paid tribute to the 63-year-old.
Chief Constable Richard Lewis said: "Paul was a much respected and loved officer and was proud of being a police officer for three decades. He worked in a number of roles for Cleveland Police including firearms, traffic and was also the sergeant responsible for the motorbike section.
“Our thoughts and condolences remain with Paul’s family and I am visiting them to offer my condolences in person. We have also offered additional support to any of our colleagues that are impacted by the loss of Paul.”
Mr Bowen, from Stockton on Tees, was riding his silver Aprilia bike and travelling south towards Helmsley when he was involved in the crash with a silver and black Norton Triton bike, ridden by Mr Dee, who was travelling in the opposite direction.
Both men tragically died at the scene.
Police are appealing to anyone who was travelling along the B1257 between Helmsley and Stokesley on Sunday morning and saw either of the motorcycles prior to the incident, or witnessed the collision itself to come forward.
Anyone with any information is asked to contact North Yorkshire Police on 101,