Spain captain Sergio Busquets was replaced during extra time so Jordi Alba was handed the armband.
And it was great to see him and Italy skipper Giorgio Chiellini having a joke as they tried to decide which end they'd take the penalties at.
Chiellini pretended to punch Alba before embracing the Barcelona left-back. Nerves, what nerves? They were about to decide who would reach the European Championship final but you'd have thought it was an Under-10s game!
ReutersCopyright: Reuters
EPACopyright: EPA
ReutersCopyright: Reuters
European heavyweights go the distance
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
This was the 10th occasion both Spain and Italy have competed in a penalty shootout at a major tournament, more than any other European nations.
Italy v Spain (10) is now the most played fixture amongst European nations in major tournament history.
This was the ninth time Italy have gone to extra time at the Euros, more than any other team, while Spain equalled the record for extra time appearances at a single edition of the competition (three - level with Portugal in 2016).
ReutersCopyright: Reuters
Wembley crowd revels in semi-final thriller
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
Fears about an empty stadium or quiet crowd proved unfounded despite tickets still being on sale during the day, and with fans unable to fly from either country without having to quarantine for too long to watch the game.
Ultimately there was a crowd of 57,811 at Wembley and they revelled in a game that went from end to end, which ebbed and flowed, before Italy came out victorious.
Sure, there were only two goals. But it didn't feel like it. It was gripping stuff. And look at these scenes at the end. Not too shabby for a Tuesday night in London.
After Alvaro Morata's penalty was saved, Jorginho strolled up to score and set up a final with either England or Denmark in London on Sunday.
Federico Chiesa looked as if he had sent Italy - who are unbeaten in 33 games - to the final in normal time with a delightful curled finish to cap off a quick counter.
But Morata stepped off the bench to slot an equaliser with 10 minutes to go after a one-two with Dani Olmo.
However, the Juventus forward's penalty miss in the shootout proved costly as Spain lost a semi-final for the first time in their history.
Today's the day
Italy and Spain produced a titanic tussle at Wembley on Tuesday to decide the first team to reach the Euro 2020 final.
Today's the day we find out who will join Italy at Wembley on Sunday - will it be England or Denmark? Can England reach their first major final since 1966?
We'll bring you all the nerves and excitement as we build up to the big game. But first, what about that first semi-final?
Live Reporting
Ben Collins and Katie Stafford
All times stated are UK
Nerves, what nerves?
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
Spain captain Sergio Busquets was replaced during extra time so Jordi Alba was handed the armband.
And it was great to see him and Italy skipper Giorgio Chiellini having a joke as they tried to decide which end they'd take the penalties at.
Chiellini pretended to punch Alba before embracing the Barcelona left-back. Nerves, what nerves? They were about to decide who would reach the European Championship final but you'd have thought it was an Under-10s game!
European heavyweights go the distance
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
Wembley crowd revels in semi-final thriller
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
Fears about an empty stadium or quiet crowd proved unfounded despite tickets still being on sale during the day, and with fans unable to fly from either country without having to quarantine for too long to watch the game.
Ultimately there was a crowd of 57,811 at Wembley and they revelled in a game that went from end to end, which ebbed and flowed, before Italy came out victorious.
Sure, there were only two goals. But it didn't feel like it. It was gripping stuff. And look at these scenes at the end. Not too shabby for a Tuesday night in London.
Italy beat Spain in shootout
Italy 1-1 Spain (AET, Italy win 4-2 on pens)
Emlyn Begley
BBC Sport
Italy beat Spain on penalties to reach the Euro 2020 final after an enthralling semi-final at a noisy Wembley.
After Alvaro Morata's penalty was saved, Jorginho strolled up to score and set up a final with either England or Denmark in London on Sunday.
Federico Chiesa looked as if he had sent Italy - who are unbeaten in 33 games - to the final in normal time with a delightful curled finish to cap off a quick counter.
But Morata stepped off the bench to slot an equaliser with 10 minutes to go after a one-two with Dani Olmo.
However, the Juventus forward's penalty miss in the shootout proved costly as Spain lost a semi-final for the first time in their history.
Today's the day
Italy and Spain produced a titanic tussle at Wembley on Tuesday to decide the first team to reach the Euro 2020 final.
Today's the day we find out who will join Italy at Wembley on Sunday - will it be England or Denmark? Can England reach their first major final since 1966?
We'll bring you all the nerves and excitement as we build up to the big game. But first, what about that first semi-final?