Previously the Met Office was only forecasting heavy thunderstorms for parts of Scotland and northern England.
A yellow warning for heavy rain has been issued for Northern Ireland this week.
Public Health England is urging people to look out for elderly relatives and friends who may be susceptible to the high temperatures and to take extra care of young children and those with heath issues.
In what is expected to be the hottest day of the year so far, with temperatures already getting close to 25 degrees, by 4pm it is expected to peak in Retford at a humid 31 degrees.
However, he warned Scotland will face thunder, lightning strikes on power transmitters, hail, gusty winds, flash floods, river flooding, property flooding, surface water and slippery roads, with two bands of heavy rain on Wednesday. Travel disruption and flooding to properties is possible if the rain becomes prolonged.
Leading first aid charity St John Ambulance is issuing the following advice to help people cope in the heatwave.
Following temperatures reaching highs of 31 degrees today, Tuesday, thunderstorms are expected to break out tomorrow morning.
The chief forecaster said: “Hot, moist air spreading north and northeast across the United Kingdom today will produce thunderstorms, initially organised within large areas of rain before becoming more isolated this afternoon”.
Met Office spokesman Grahame Madge said: “The whole of the area that is covered by the warning can anticipate some thundery outbreaks”.
Thursday is expected to see cooler weather, with fresher conditions from the Atlantic bringing temperatures down to the comfortable mid-20s.