The mercury reached 45.9 degrees Celsius (114.6 Fahrenheit) in Gallargues-le-Montueux in the Gard department in southern France, according to the French national weather service Météo-France.
This is 1.8 degrees higher than the previous record from 2003.
Around 4,000 French schools were closed on Friday and the opening hours of parks and public swimming pools were extended.
French authorities have taken a number of radical steps this week to prevent a repeat of the tragic consequences of the 2003 heat wave that left around 14,000 people dead.
Paris activated its heat emergency plan last weekend, put together in the aftermath of the 2003 heat wave. Cooling rooms were opened in some municipal buildings and mist showers were installed in the streets.
Climate scientists have warned that heat waves such as this one are becoming more frequent and increasingly severe because of the climate crisis. Météo-France said the frequency of such events is expected to double by 2050.
Europe has been battling the heat all week, with Germany, Poland and the Czech Republic each recording their highest-ever June temperatures on Wednesday.
The German Weather Service said temperature of 38.6 degrees Celsius (101.5 Fahrenheit) was recorded at 2:50 p.m. local time on Wednesday in Coschen, on the country’s border with Poland.
The previous record stood at 38.5 Celsius (101.3 Fahrenheit), which was measured in 1947 in Bühlertal, which lies close to France.