Staff at every ambulance service except one across the country will go on strike on March 8, Unison has announced.
Up to 32,000 NHS workers at the union - including nurses, blood collection workers, healthcare assistants, cleaners and porters - will down tools on the new March date.
Unison accused the Government of a "pick-and-mix solution" after it emerged Health Secretary Steve Barclay would be holding talks with the Royal College of Nursing on pay.
It said five NHS unions are involved in strike action over pay, staffing and patient care, as it slammed: ""Choosing to speak to one union and not others won't stop the strikes and could make a bad situation much worse."
But the missing-in-action Health Secretary did not attend talks today with the British Medical Association (BMA) in an effort to break the deadlock over upcoming junior doctor strikes.
Thousands more NHS workers are now joining Unison's strike action following the re-balloting of ten NHS employers in England, where the strike vote fell just short of the legal threshold last year.
It is a huge escalation of the dispute - which Unison said was "a direct result of the government’s failure to hold proper pay talks with health unions".
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.
They’ll be joined by ambulance staff at four services in England – South Central, East of England, West Midlands and East Midlands, also now able to take action following their successful strike vote last week.
Colleagues working for other ambulance services, which have already taken strike action, will also walk out on the same day.
South East Coast Ambulance Service will be the only place where paramedics are not going on strike.
Emergency care is guaranteed during strike action.
Unison's general secretary Christina McAnea said: "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.
"Next month staff in all but one of the ambulance services in England will walk out. They'll be joined by thousands more NHS colleagues, many striking for the first time. The action by NHS Blood and Transport Staff will hit blood collection across the country too.
"The government now has several billion pounds more than it thought it had in its coffers. Now he has the cash, Rishi Sunak must speak to everyone involved if the dispute is to end.
"Governments elsewhere in the UK know how pay deals can be done. Rishi Sunak must copy their example, hold proper pay talks and allow everyone to get back to work."
The GMB union, which represents NHS staff from porters to paramedics, has further national ambulance strikes pencilled in for March 6 and 20.
Dr Rob Laurenson and Dr Vivek Trivedi, co-chairs of the BMA's junior doctors’ committee, said today: “We have held discussions with the Health Secretary’s officials today.
"We are very disappointed that Steve Barclay decided not to attend. There was no offer on the table and the Department made it clear they are not ready to enter negotiations but we left the Department of Health civil servants in no doubt that it is still not too late to avert a strike by tens of thousands of junior doctors in England."
They said they had written to Mr Barclay calling for a meeting, adding that he had "dragged his heels for far too long".
