The union said over 2,600 ambulance workers in the West Midlands, North West, North East, East Midlands and Wales will take strike action in late January.
The strike would coincide with a similar walkout by ambulance workers with the Unison union on Jan. 23.
Unite's general secretary Sharon Graham said ambulance workers had been left with no option and blamed the government for its failure intervene to end the dispute.
British Prime Minister Rishi Sunak said he was hoping for constructive talks with trade union leaders next week and wanted to have "to have a grown up, honest conversation".
"The talks the government has lined up for Monday yet again look like nothing more than a smoke screen and are clearly not a negotiation on NHS pay," Graham said in statement.
Thousands of workers in various sectors, including rail, teaching and healthcare have announced strike action in disputes over pay.
The government announced plans to bring in legislation to make key public services like ambulances services maintain minimum safety levels during industrial action by staff.
(Reporting by Sachin Ravikumar and Farouq Suleiman; editing by Alistair Smout)
