And a yellow weather warning for thunderstorms is in place for much of the country from Thursday to Saturday, warning of disruption due to flooding, lightning strikes, hail and wind.
Met Office Chief Meteorologist Steve Willington, said: “Although many areas will enjoy dry and sunny weather over the next few days, the high temperatures will trigger thunderstorms which may cause flooding and disruption in a few places."
The temperature in London around 3pm on Thursday hit 33.3C, breaking the record set the day before, the Met Office said.
"Heathrow has matched yesterday's 32.6C and is likely to rise further this afternoon," the Met Office tweeted at 2pm.
The temperature then climbed to 33.3C an hour later.
Beachgoers travelled to the water in huge numbers again on Thursday.
Camber Sands beach was so popular that police were forced to close the road leading to the shore at 10.30am due to heavy traffic.
An air ambulance helicopter landed on the beach around noon after the woman suffered a "medical episode" according to police.
The Met Office raised its heat alert level to three and health authorities urged sun seekers to protect themselves amid the "exceptionally hot weather forecast this week".
Forecaster also warned people can get sunburnt in just 15 minutes.
Public Health England said older people, those with underlying health conditions, and very young children were all more at risk from the higher temperatures.
People have been advised to keep cool and stay hydrated where possible.
Ultra-violet rays were expected to reach level nine across parts of Devon and Cornwall.
Met Office meteorologist Alex Burkill said that UV levels would "reach eight across many places and would reach nine across parts of Devon and Cornwall".
He said: "That's about as high as it gets really in the UK. The sun is as strong as it gets at the moment because we're so close to the solstice.
"We've got peak sun strength, clear skies, plenty of sunshine - they're the perfect ingredients for high UV."
Emer O'Connell, consultant in public health at PHE, said it was important that people kept checking on the vulnerable, as many continued to spend more time at home due to coronavirus.