Thousands of ambulance staff across five services in England - London, Yorkshire, the South West, North East and North West - will walk out on Friday 10 February, Unison says.
It means strikes over pay will now be happening across the NHS every day next week, apart from Wednesday.
Life-threatening 999 calls will be attended to but others may not be.
Downing Street says the continuing industrial action will concern the public.
The NHS's biggest day of industrial action is set to happen on 6 February, when many nurses and ambulance crews across England and Wales will be on strike.
Unison says the government must stop "pretending the strikes will simply go away" and act decisively to end the dispute by improving pay.
The union warned that unless the government had a "major rethink" over NHS pay, and got involved in "actual talks" with unions, it would announce strike dates running into March.
The government says the above-inflation pay rises requested are unaffordable.
Source: BBC News, 31 January 2023
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