Alan Mort, 63, from Kinmel Bay, Conwy, suffered head injuries and died in hospital after the incident on the A548 near Manor Industrial Estate, Flint.
Mr Mort, who was a member of Chester and North Wales CTC and a clinical team leader for North Wales Ambulance Trust, was described as "greatly respected".
A 44-year-old man has been arrested and released on police bail. The collision occurred at 12:38 GMT on Sunday and the road was closed in both directions.
Police are appealing for witnesses, particularly anyone who saw a cyclist or silver Range Rover in the area. Officers said the arrested man was the driver of the vehicle involved.
A Welsh Ambulance Service spokesperson said: "We are shocked and saddened by the tragic death of Alan and our thoughts are with his family at this sad time. Alan was greatly respected not just by his former colleagues in Flintshire, but by staff across north Wales. He was a kind and gentle man who brought great compassion and care to the patients he treated during his time in the ambulance service. He was a role model to many of our current staff and will be sadly missed by all."