Union members at ambulance trusts in the West Midlands, North West, South Central, South Coastal, and East Midlands had planned to strike on March 6 and March 8.
However, the Unite union paused the strike action on Sunday afternoon in order to enter pay talks with the government.
It comes after Unison and GMB unions cancelled industrial action which would have involved tens of thousands of key workers.
Unite head of operations Gail Cartmail said: “Following further assurances from the government over the weekend, Unite has in good faith agreed to pause the strike action.
“If the meeting doesn’t meet these assurances strike action will resume.”
The union said the assurances relate to confirmation that any deal will include new money, rather than placing further pressure on NHS budgets and an indication discussions will not impact the conditions on health staff.
Talks are expected early this week.
It would have marked the first time that Unite members in South Central and South Coastal had taken industrial action.
Members in Yorkshire, who are also planning to strike for the first time, were due to take industrial action on Wednesday.
Unite had also called off strikes in Wales on March 6 due to pay talks continuing with the Welsh Government.
On Friday, Unison and GMB unions called off a walkout that would have involved tens of thousands of ambulance workers on Monday and Wednesday.
Unison and GMB made the decision after the Department for Health and Social Care (DHSC) said money was available for potential pay rises covering this year and next.
Some 32,000 NHS workers would have been involved in planned Unison strikes – including 24,500 ambulance staff – while 13,000 ambulance workers were part of the GMB action.
A Department of Health and Social Care spokesperson said: “We’re pleased that unions representing the majority of ambulance workers, nurses, physiotherapists, porters, cleaners and other non-medical staff have agreed to pause strikes and enter a process of intensive talks. “We want to find a fair and reasonable settlement that recognises the vital role of NHS workers, the wider economic pressures facing the UK and the prime minister’s priority to halve inflation.”
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