The Parkway and Birley Moor stations in Sheffield, Barnsley station, Aston Park in Rotherham and Edlington in Doncaster will be used as a base for an ambulance and paramedics.
The link up between South Yorkshire Fire and Rescue and Yorkshire Ambulance Service is believed to be one of the first schemes of its kind in the country.
Deputy Chief Fire Officer, John Roberts, said: “This is the best possible proof of our commitment to pursue meaningful collaboration opportunities with our emergency service partners.
“This agreement makes perfect sense for us, for the ambulance service and for the taxpayer. By working alongside each other, the move will also benefit both organisations by improving how we work together to solve problems we both face.”
Jackie Cole, of Yorkshire Ambulance Service, said: “Our staff often work together at incidents across the county and this opportunity means that our close working relationship will be further endorsed.
"Our vehicles operate from a network of strategically located stand-by points and the locations of some of South Yorkshire Fire and Rescue's stations are well matched to where our resources need to operate from to serve local communities and provide responsive patient care.”
The fire service is looking at whether it can share more buildings with South Yorkshire Police.
Maltby police station is to be modified to house a fire engine and firefighters when Maltby fire station closes.