Crews from St John's Ambulance will begin responding to 999 calls across the country, including in the East of England.
The plan which came into force today, will see the charity provide support to England's 10 NHS ambulance trusts, has been announced in a bid to combat the health service's deterioration in response times.
The deal has seen the NHS sign a £30million contract with St John for the organisation to act as an ambulance auxiliary service.
Crews are expected to deliver at least 5,000 hours of support per month, equating to more than 400 12-hour shifts.
Professor Sir Stephen Powis, NHS national medical director, said: "The new Ambulance Auxiliary Service helps to build on the vital role played by St John Ambulance since the formation of the health service and will complement existing services.
“This new agreement with one of our longest partners is a welcome addition as the NHS does everything it can to boost capacity ahead of what is set to be another difficult winter.”
A report in June revealed emergency ambulance response times for Category 2 emergencies in the East of England were more than double the national target.
It is hoped the 800 ambulance crew members, both employees and volunteers, and over 250 ambulances belonging to St John's nationwide will go a long way in helping to lower response times over the next four years.
The charity's deputy chief executive and chief operating officer, Richard Lee, said: "St John has always supported the health service through emergency ambulance provision during peak periods and seasonal demands, but this new contract gives the vital relationship between our charity and NHS England firm foundations for the future.
“This evolution of our longstanding relationship with the health service enables us to put in the additional long-term planning and investment in people and fleet that’s required to live up to our mission of being an ambulance auxiliary that can be relied upon every time."
Health and social care secretary, Steve Barclay, said: “St John Ambulance’s 800 crew members have invaluable experience on the frontline and have worked hand in hand with our emergency services to keep patients safe in the past – delivering approximately 200,000 hours of support across England during the pandemic, providing extra resilience to ambulance services when needed, and supporting A&E departments during major emergencies."
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