Ambulance chiefs have warned people not to underestimate the heat, even if temperatures drop slightly.
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Welsh Ambulance Service said there is still a "very real danger," especially for those with asthma or angina.
Wales experienced its warmest night ever on Monday, while on Tuesday the temperature in Hawarden, Flintshire reached 36.2C (97.2F).
This is provisionally the second hottest day on record in Wales.
Overnight on Monday, the temperature was a minimum 24.5C (76F) in Aberporth, Ceredigion, beating the previous night time high of 22.2C (72F) from 1948.
By midday on Tuesday, temperatures had reached 34.2C (93.6F) at Rhyl, Denbighshire.
Welsh Ambulance Service reported a rise in demand and challenges in handing over patients at hospital.
Lee Brooks, operations director, said the intense heat could be a danger to otherwise healthy people.
"A high proportion of calls yesterday were reporting breathing problems and chest pain," he said.
"We also picked up that hydration is an issue for some patients."
Aneurin Bevan University Health Board said it was experiencing unprecedented demand.
"The addition of the extreme heat in recent days has further exasperated this pressure," a spokesman said.
Welsh Water said another record also went on Monday - with people across the country using more water than on any other day.
This was an increase of 40% compared with normal usage in some areas.
