Italy ended Spain’s reign as champion of Europe when the Azzuris claimed a famous 2-0 win in Paris.
Italy produced a fine performance to set up a quarterfinal tie with world champion Germany.
Giorgio Chiellini's 33rd-minute goal gave Italy the lead, and Graziano Pelle smashed home a second in stoppage time to seal the win.
For eight years, Spain has enjoyed its role as champion of Europe but it had no answer to an Italian team set up brilliantly by coach Antonio Conte.
De Gea pulled off a string of fine saves to deny the likes of Pelle, Emanuele Giaccherini and Eder but Italian class told in the end as they underlined their emergence as genuine contenders to seize the vacated crown.
Spain had seemed under the weather from the first minute, which was greeted by a torrential downpour, and De Gea was soon called into action with an excellent diving save to stop Pelle's well-directed free-kick.