Mikel Oyarzabal continued his pair of semi-final assists against Italy with Spain’s opening goal, but Karim Benzema quickly hit back before Mbappe’s winner.
It was a second consecutive victory for Didier Deschamps’ side after their thrilling 3-2 semi-final success against Belgium.
Hugo Lloris saved easily from Pablo Sarabia at the other end, while Azpilicueta again thwarted Benzema with a key block.
French defender Jules Kounde survived a referral from VAR for a possible handball in the penalty area and Marcos Alonso then completed a free kick right next to Lloris, expecting a helpless cross.
The Blues lost defender Raphael Varane to injury just before half-time, in a blow to his club, Manchester United. Dayot Upamecano took his place.
Theo Hernandez, who scored France’s late winner against Belgium on Thursday, was crossbar width not to repeat the feat, but instead Spain broke the other end and Oyarzabal hung on to Sergio Busquets’ long pass, faced Upamecano and scored in the 64th minute.
However, France were tied two minutes later as Pogba and Mbappe combined to create luck and Benzema brilliantly curled up at home from a narrow angle.
And they got their full reward when Mbappe delayed his run to head for Hernandez’s deep ball and clinically finish under Simon, with the goal held by VAR after an offside check.
Lloris brilliantly saved from Oyarzabal’s volley, while Simon denied Mbappe a third which would have been tough for Spain.
Simon was ahead for corners in the extra five minutes, but Lloris’ stoppage on substitute Yeremi Pino smothered Spain’s last hope.
After Thibaut Courtois refused Federico Chiesa in another goalless first half, Nicolo Barella took the Azzurri back in front in the first minute of the second period and Berardi doubled his lead after Leicester’s Timothy Castagne committed a fault on Chiesa.
Belgium touched the wood by Alexis Saelemaekers in the first half and Michy Batshuayi and Yannick Carrasco in the second, but had to wait until the 86th minute to reverse Charles De Ketelaere’s first international goal.