Plans are already in place for some local trains to operate at reduced speed, and the TUC said that commuters and workers should be given flexibility at times of high temperatures.
"It is no fun working in a baking office or factory and employers should do all they can to take the temperature down," said TUC general secretary Frances O'Grady.
"Clearly vest tops and shorts are not suitable attire for all frontline staff, but those not dealing with the public should be able to discard their tights, ties and suits."
The Chartered Management Institute echoed the TUC's call for flexible working, claiming that many businesses underestimated the effect that weather conditions could have on output.
"It is therefore vital for employers to ensure they have business continuity plans in place to prepare for these situations, to ensure that productivity doesn't drop and that flexible working arrangements are on offer, should employees require these," it said.