The tragedy happened on the A49 at about 8am yesterday and the victim, a man, was confirmed dead at the scene.
Multiple resources attended the incident at the junction of Moreton Road in Herefordshire, including two emergency ambulance crews, paramedic officers, the Midlands Air Ambulance from Strensham and two Mercia Accident Rescue Service doctors, as well as West Mercia Police.
The man's crew mate, the driver, was taken to hospital and has since been discharged.
A West Midlands Ambulance Service spokeswoman said: “Sadly, despite everyone’s best efforts, nothing could be done to save our colleague, who was the front passenger, and he was confirmed dead at the scene.
“His crewmate, the driver, was also injured in the incident. He has received treatment at hospital and has subsequently been discharged.”
West Midlands Ambulance Service Chief Executive, Anthony Marsh, said: “This is truly awful news, and my thoughts and prayers go out to the family, friends, and colleagues of those involved at this very difficult time.
"I am enormously proud of all the staff and the university students as part of their clinical placement that worked so hard and professionally to try to save our colleague.
"I am sorry that despite their best efforts, he could not be saved.”
A spokesman for West Mercia Police said: "We were called at around 8am to reports of an incident near the junction of Moreton Road, towards Leominster, involving an ambulance vehicle whilst on route to a 999 call.
"Sadly the technician in the passenger’s side of the vehicle was pronounced dead at the scene despite the efforts of the emergency services who attended.
"Our thoughts are with the deceased’s love ones and our colleagues in West Midlands Ambulance Service at this difficult time."
Anyone who may have seen the incident or have dashcam footage should contact the police on 101, quoting incident 00101i of April 24.