Mercury reached 45.1 degrees Celsius (113.2 Fahrenheit) just before. local time in Villevieille, in the Gard department of southern France, according to the French national weather survey Meteo-France.
This is 1 degree higher than the previous record from 2003.
About 4,000 French schools were closed on Friday and the opening hours for parks and public swimming pools were expanded.
The French authorities have taken a number of radical steps this week to prevent repetition of the tragic consequences of the 2003 heat wave that left about 14,000 people dead.
Paris activated its heating plan last weekend, put together in the aftermath of the 2003 heat wave. Cold rooms were opened in some municipal buildings and fogs were installed in the streets.
Climate scientists have warned that heat waves like this will become more frequent and more severe due to the climate crisis. Météo-France said the frequency of such events is expected to double by 2050.
Europe has been fighting for the heat all week. Germany, Poland and the Czech Republic record their highest June temperatures on Wednesday.
The German weather service said a temperature of 38.6 degrees Celsius (101.5 Fahrenheit) was recorded at. 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 is close to France.
While temperatures around 100 degrees Fahrenheit may not work too high, they are well above the seasonal average for the region, and episodes of intense hot weather are more common in July and August.
The heat wave is also unusual due to its timing. Such intense hot weather episodes are more common in July and August.
Besides that, many European cities are not designed to handle such temperatures. Air conditioning is less common and public transport systems often struggle.
CNN's Antoine Crouin helped report.