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London Ambulance Service (LAS) workers are to vote on whether to strike in a dispute over pay.
The GMB Union said its 1,500 LAS members would be balloted, after a consultative ballot saw 91% of employees vote in favour of action.
The union claimed the government's 4% pay rise would leave workers facing a real terms pay cut.
The Department for Health urged the union to "consider the potential impact on patients".
GMB Organiser Lola McEvoy said members had been "forced to take a stand in order to protect patient care" and added that ballot dates would be announced later in the week.
The union has also announced a formal strike ballot in Yorkshire, North East, West and East Midlands, North West and East of England ambulance services.
Ms McEvoy said: "Ambulance workers are leaving trusts in droves, because the workload pressure is too much and the pay is too poor.
"They do not take industrial action lightly and it is always a last resort - but things can't go on like this.
"Something has to give," Ms McEvoy added.
A spokesman for the Department for Health said: "We are giving over 1 million NHS workers a pay rise of at least £1,400 this year, as recommended by the independent NHS Pay Review Body.
"Industrial action is a matter for unions, and we urge them to carefully consider the potential impacts on patients."