Ambulances stood on standby near tourist hotspots and regions issued fire warnings as experts warned that such heatwaves, intensified by climate change, would become more frequent.
Peaks of 43 degrees Celsius (109 Fahrenheit) were expected in areas of southern Spain and Portugal, while nearly all of France is sweltering in heat expected to last for several days.
In Italy, 21 cities were on high alert for extreme heat, including Milan, Naples, Venice, Florence and Rome.
"We were supposed to be visiting the Colosseum, but my mum nearly fainted," said British tourist Anna Becker, who had travelled to Rome from a "muggy, miserable" Verona.
Hospital emergency departments across Italy have reported an uptick in heatstroke cases, according to Mario Guarino, vice president of the Italian Society of Emergency Medicine.
"We've seen around a 10 percent increase, mainly in cities that not only have very high temperatures but also a higher humidity rate. It is mainly elderly people, cancer patients or homeless people, presenting with dehydration, heat stroke, fatigue," he told AFP.
- 'Climate shelters' -
Hospitals like the Ospedale dei Colli in Naples have set up dedicated heatstroke pathways to speed access to vital treatments like cold water immersion, Guarino said.
In Venice, authorities offered free guided tours for people over 75s in air-conditioned museums and public buildings.
Bologna has set up seven "climate shelters" with air conditioning and drinking water, Florence has called on doctors to flag up the lonely and vulnerable, Ancona is delivering dehumidifiers to the needy, and Rome has offered free access to city swimming pools for those over 70.
Scientists say climate change is stoking hotter and more intense heatwaves, particularly in cities where the so-called "urban heat island" effect amplifies temperatures among tightly packed buildings.
"The heat waves in the Mediterranean region have become more frequent and more intense in recent years, with peaks of 37 degrees or even more in cities, where the urban heat island effect raises the temperatures even further," said Emanuela Piervitali, a researcher at the Italian Institute for Environmental Protection and Research (ISPRA).
"A further increase in temperature and heat extremes is expected in the future, so we will have to get used to temperatures with peaks even higher than those we are experiencing now," she told AFP.
- Invasive species -
In Portugal, several areas in the southern half of the country, including the capital Lisbon, are under a red warning for heat until Monday night due to "persistently extremely high maximum temperature values", according to the Portuguese Institute for Sea and Atmosphere (IPMA).
Two-thirds of Portugal was on high alert Sunday for extreme heat and forest fires, as was the Italian island of Sicily, where firefighters tackled 15 blazes Saturday.
In France, experts warned that the heat was also severely impacting biodiversity.
"With this stifling heat, the temperature can exceed 40 degrees in some nests," said Allain Bougrain-Dubourg, president of the League for the Protection of Birds (LPO).
"We are taking in birds in difficulty everywhere; our seven care centres are saturated," he said.
It is also attracting invasive species, which are thriving in the more tropical climes.
Italy's ISPRA launched a campaign this week urging fishermen and tourists alike to report sightings of four "potentially dangerous" venomous species.
The lionfish, silver-cheeked toadfish, dusky spinefoot and marbled spinefoot are beginning to appear in waters off southern Italy as the Mediterranean warms, it said.
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