Stephen Lewis, 41, was involved in a collision with a Skoda Citigo near Ilfracombe, north Devon, on Monday.
Emergency services were called to Ridge Hill at Combe Martin around 07:30 BST.
Mr Lewis, described as a "great ambassador" for South Wales Police, suffered serious injuries and was pronounced dead at North Devon District Hospital.
Another rider, a 43-year-old man, cycling with Mr Lewis was treated for minor injuries, while the female driver of the car was not hurt.
Colleagues have paid tribute to Mr Lewis, who was stationed within the community safety team at Neath, Neath Port Talbot.
Western divisional commander Ch Supt Joe Ruddy said he was "hard working, enthusiastic" and someone "who loved helping people".
"Steve was a hugely respected member of the team and everyone is shocked and saddened to hear of his death in such tragic circumstances. Our thoughts are with his family, friends and colleagues at this very sad time," he added.
Devon and Cornwall Police is investigating the collision and has appealed for witnesses.
A police community support officer from south Wales has died following a crash while cycling on a family holiday.