Penalties, tiki-taka and the Divine Ponytail: Italy v Spain is a modern classic
Here AFP Sport looks at their most memorable clashes as the two sides prepare to do battle for the fifth time in as many Euros, with top spot in Group B up for grabs:
Divine Baggio sinks Spain at USA '94
Few Italian players have captured the imagination of the football public quite like the "Divine Ponytail" Roberto Baggio, who lit up the 1994 World Cup and scored the decisive goal in a quarter-final battle with Spain.
After Dino Baggio put Italy ahead with a rocket of a shot in the 25th minute in Foxborough, Jose Luis Caminero's deflected strike levelled the scores just before the hour.
With the match looking destined for extra time Roberto Baggio fired Italy into the last four by collecting Giuseppe Signori's lofted pass, skipping around Andoni Zubizarreta and drilling home a perfect finish.
Baggio suffered a tragic end to his remarkable tournament as his missed penalty in the final with Brazil cost the Azzurri the World Cup.
Casillas wins clash of titans with Buffon
Two years after winning the World Cup in a penalty shoot-out victory against France, it was Italy's turn for heartbreak as they fell to Spain in the quarter-finals of Euro 2008.
Iker Casillas earned eventual tournament winners Spain a spot-kick victory at the Ernst Happel Stadion in Vienna against Gianluigi Buffon's Italy after a gruelling match which finished goalless.
Casillas and Buffon were considered the two best goalkeepers in the world at the time, with both captaining their respective national teams.
Real Madrid icon Casillas kept out attempts from Daniele De Rossi and Antonio Di Natale while Buffon failed to stop a single Spanish penalty as Luis Aragones' side progressed and went on to dominate international football for the next four years.
Tiki-taka sweeps Italy aside
Spain got the better of Italy again four years later as an awesome display of tiki-taka football made La Roja the first team ever to retain a European Championship title.
Already reigning world champions, Spain confirmed their status as the pre-eminent force in world football by thumping an Italy team containing Buffon, Giorgio Chiellini, Andrea Pirlo and an inspired Mario Balotelli 4-0 in a one-sided final in Kyiv.
Barcelona midfield trio Xavi, Andres Iniesta and Sergio Busquets passed teams to death in what turned out to be that generation's last hurrah on the international stage, as Spain won the Euros while only conceding one goal in open play all tournament.
That goal was scored by Di Natale in the 1-1 draw which started both Spain and Italy's Euros campaign.
Donnarumma saves Italy
Gianluigi Donnarumma got some revenge for Buffon three years ago when his saves sent Italy past Spain and into the Euro 2020 final, where the Azzurri would win a thrilling final against England.
Another exciting match went to penalties after Alvaro Morata struck with 10 minutes remaining to cancel out Federico Chiesa's brilliant opener for the Italians.
Donnarumma was the hero of a feverish night at Wembley as he saved Dani Olmo's opening penalty before denying Morata, allowing Jorginho to send Italy to the final with a nonchalant spot-kick.
The Paris Saint-Germain goalkeeper would step up again in another shoot-out in the final as Italy won the Euros for the first time in over half a century.