Heatwave: the UK passes 40C Fires blaze for the first time
Thermometers hit 40.3C at Coningsby in Lincolnshire, while 33 other locations exceeded the UK's previous highest temperature of 38.7C, set in 2019.
Several fire services declared major incidents after a surge in fires. A significant blaze in Wennington, in east London, left homes gutted.
Some rail services were cancelled after tracks overheated or buckled and overhead cables failed.
Hundreds of firefighters tackled fires across London, including in Wennington, where a grass fire spread to properties.
Residents, who had to be evacuated, told the BBC that eight homes and possibly a local church had been destroyed in the fire, while one firefighter at the scene described it as "absolute hell".
Tim Stark, who alerted the fire brigade and whose own house was destroyed in the blaze, spotted the fire in his neighbour's garden but despite their best efforts with a hose and watering can, had been unable to stop it spreading amid the dry conditions.
"I reckon about 15-20 houses might be gone, or uninhabitable," he said.
"My house is completely gone, as is the next door neighbour's and three or four other houses along that bit."
There have also been fires elsewhere in the country with major incidents declared in Leicestershire, East, North and South Yorkshire and Lincolnshire, Hertfordshire, Suffolk and Norfolk.
Home Secretary Priti Patel said she had been updated on the "dangerous fires" and urged the public to follow safety advice from their local fire service.
In the capital, people were urged not to have barbecues or bonfires and to be careful when disposing of cigarettes.
Two people were taken to hospital to be treated for smoke inhalation after a fire in Dagenham, east London, while further north a nursery was caught in a blaze in Milton Keynes.
London Fire Brigade assistant commissioner Jonathan Smith said some of the fires in the city were the result of "tinderbox" conditions and said Tuesday evening would be "critical" in ensuring the fires were kept under control.
"It would be premature to say we are out the other end of this incident," he added.
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