Jeremy Daw, known to friends as Jack, died on Saturday morning at the junction of Moreton Road and the A49 in Herefordshire.
West Midlands Ambulance Service's emergency operations delivery director, Nathan Hudson, has said he was "one of life's good guys".
Mr Hudson also said the tragedy appeared to be the result of a "tragic accident".
He said Mr Daw, of Hereford, retired as a paramedic in November 2020 before rejoining as a technician in January this year to "support the trust during the pandemic".
He was in the front passenger seat of the ambulance, which was responding to a 999 call at the time of the tragedy, West Midlands Ambulance Service said.
Speaking about the incident, Mr Hudson said: "We had a 999 call where the crew responded yesterday shortly before 8am.
"About a minute after eight we had a 999 call to say the crew had been involved in an incident, whereby an object of some description had gone through and pierced the windscreen and one of the crew members were unconscious.
"The driver of the vehicle, who was also injured, was able to get out and try and help and support Jack because he was unconscious and started life-saving treatment to try and resuscitate him."
He added: "We don't think this was malicious, we think this is a tragic accident."
Mr Hudson said: "He was a remarkable character. He was one of life's good guys and he will be sorely missed in and around Hereford."
It is not yet known what caused the incident.
Police appeared to retrieve what seemed to be a large piece of rock from the scene, but nothing has been confirmed.
West Mercia Police said the ambulance was travelling towards Leominster at the time of the incident.
The Midlands Air Ambulance, two emergency ambulance crews and paramedic officers attended the incident.
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."
West Mercia Police are asking anyone who may have seen the incident or have dashcam footage to contact them on 101 quoting incident 00101i of 24 April.