Temperatures climbed to a record-breaking 48.8 degrees in Syracuse, located on the island’s south-east coast, on Wednesday, according to Sicily’s Agrometeorological Information System (SIAS).
Athens previously held the record title for the hottest temperature in Europe at 48C, accepted by World Meteorological Organisation (WMO).
As temperatures soared, fires have continued to ravage southern Italy on Wednesday.
Blazes have been sweeping through Sicily and Calabria.
Firefighters said they had been on the ground working on more than 3,000 operations in Sicily and Calabria in the last 12 hours.
"We must immediately respond to this emergency, providing economic relief to those who have lost everything," said Agriculture Minister Stefano Patuanelli.
Fires have been sparked across southern Europe amid the rising temperatures.
Italian island of Sardinia has suffered damage to the landscape following the blazes.
Many villages in Greece have been evaculated as firefighters continue to battle the wildfires.
Duncan Scott, a Scottish meteorologist, issued a stark warning about the weather after the news broke about the record-breaking temperatures.
“A dangerous heatwave spanning much of North Africa and into Southern Europe is unfolding right now. The focus of heat will shift west and north slightly in the coming days. More records are inevitable,” he said.
