Ambulance and other health workers in Unison will strike on March 8 in an escalation of the long-running dispute over pay, the union announced.
The strike will include members of the London Ambulance Service.
It comes after nursing strikes scheduled to take place next Wednesday were paused after the Government announced that it would hold “intensive talks” with the Royal College of Nursing.
Unison’s announcement suggests that strikes affecting other health workers - including paramedics, call handlers and physiotherapists - will proceed regardless of the breakthrough with the nursing union.
Health workers at NHS Blood and Transplant, Great Ormond Street Hospital, the Tavistock and Portman NHS Foundation Trust, Liverpool Women’s Hospital and the Bridgewater Community Trust will now be among those now walking out for the first time, Unison said.
It will also include ambulance staff at four services in England – South Central, East of England, West Midlands and East Midlands - following a re-ballot last week. This is in addition to staff in London, orkshire, the North East, North West and South West who have already staged four days of industrial action.
Unison’s general secretary Christina McAnea said: "Unfortunately for patients, staff and anyone that cares about the NHS, the strikes go on.
"There can be no pick-and-mix solution. NHS workers in five unions are involved in strike action over pay, staffing and patient care.
"Choosing to speak to one union and not others won't stop the strikes and could make a bad situation much worse.
"The entire NHS team is absolutely determined to stand firm for better patient care. They’ll be furious at the government’s failure to invite their union in for talks. Not least because a deal just for nurses cannot possibly work, and nurses belong to other unions too.”
She added: "By holding solo talks, the prime minister is condemning patients to many more months of disruption. Health workers will want assurances from ministers that they have no intention of ripping up pay agreements in the NHS. Any attempt to do so, would be an incredibly serious move.
Ms McAnnea said that Mr Sunak’s Government “must speak to everyone involved if the dispute is to end”.
It comes as the Department for Health and Social Care (DHSC) submitted its evidence to the NHS Pay Review Body for the 2023/24 financial year.
Officials said a 3.5 per cent pay rise for staff would be affordable for the UK Government.
Unite said the Government’s proposal on NHS pay will accelerate a spring of strikes across the health service.