The warning is in place from midnight on Sunday until 11.59pm that night, on a day when temperatures are predicted to soar further, but the forecaster added the warning could be extended to Monday next week.
The Met Office said temperatures could rise to in excess of 35C in the southeast on Sunday and more widely to 32C within the warning area, which is likely to have adverse health effects for the public, not just limited to the most vulnerable.
The warning is being enforced across the east Midlands, east of England, London, southeast, northeast, northwest, southwest, wales, west Midlands and the Yorkshire and Humber region.
A statement from the Met Office said: "Population-wide adverse health effects are likely to be experienced, not limited to those most vulnerable to extreme heat, leading to potential serious illness or danger to life. Government advice is that 999 services should be used in emergencies only; seek advice from 111 if you need non-emergency health advice.
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