I don't know exactly where to look for data about whole Italy...
But around my place the record should be the 29,4 °C recorded in Brossasco (near Cuneo) the 01/17/2007.
According to wikipedia, the most of the record high temperatures recorded in my region (Piedmont) were recorded during the same heatwave. In practice this time the foehn wind was particularly strong.
Ondata di caldo del gennaio 2007 - Wikipedia
the page is in Italian, but I just want to show you the table (1st column = town, 2nd column altitude, 3rd column temperature).
Now let's see if I can find something else about the rest of Italy...
ok, I've found that the 01/02/1962 was recorded a temperature of 30.4°C in Palermo (from the "Osservatorio Astronomico di Palermo" = Palermo's astronomical observatory). But I'm not 100% sure that it is the absolute record for all the country.