The Fire Brigades Union (FBU) said 32,500 of its members across the UK will vote in the next few weeks on whether to launch a campaign of industrial action.
The union said the move follows a two percent pay offer made in June, which has not been increased despite the soaring rate of inflation.
The FBU said the pay offer represents a “significant real-terms pay cut”.
The ballot is expected to be held in five weeks’ time – and will present yet another challenge to incoming Prime Minister Liz Truss.
An electrified fire engine which is to be deployed in the UK for the first time
Sophia Macias/London Fire Brigade
Liz Truss is set to take over as Prime Minister
Victoria Jones
The announcement was made just hours before the new PM takes office, and follows a wave of industrial action this summer by tens of thousands of workers.
FBU general secretary Matt Wrack said: “Taking strike action is always a last resort but our employers are increasingly leaving us with no choice.
“There is huge anger among firefighters at falling pay.
“Firefighters must be paid fairly – there is absolutely no question when it comes to this.
“It is the responsibility of fire service employers to provide decent pay offers and that has not happened.
“The ball is now in the fire service employers’ court. It is not too late for them to make a much better pay offer for consideration by our members.”
Firefighters went on strike over pensions almost a decade ago and there was a lengthy strike over pay almost 20 years ago.