Luke Shaw's early goal was cancelled out in normal time by Leonardo Bonucci's equaliser with the game eventually going to extra-time and penalties.
Marcus Rashford, Jadon Sancho and Bukayo Saka missed the decisive spot kicks to give Italy a first European Championship win since 1968.
Manager Gareth Southgate confirmed afterwards that the identities of the five takers was his decision, with his choices subsequently coming in for criticism in the wake of the defeat.
"If you're (Raheem) Sterling or (Jack) Grealish, you cannot sit there and have a young kid [Saka] go up for a penalty ahead of you, you can't," former Manchester United captain Roy Keane told ITV.
"You cannot let a shy 19-year-old go up in front of you. They have a lot more experience, Sterling has won trophies, they had to get in front of the young kid and stand up."
Grealish though has responded to Keane insisting he did want to take one.
"I said I wanted to take one!!!!," he wrote on Twitter. "The gaffer has made so many right decisions through this tournament and he did tonight! But I won’t have people say that I didn’t want to take a peno when I said I will…"
Roma manager Jose Mourinho took a similar stance to Keane and felt more experienced England players should have been taking a spot-kick.
The Roma manager told Talksport: "The decision of the penalty takers, I think it is hard to leave Saka as the last one. I think it is hard for a kid to have everything on his shoulders at that moment. I just feel very sorry for him.
"In this situation where was (Raheeem) Sterling, where was (John) Stones, where was (Luke) Shaw?
"I feel that Gareth is such an honest guy. Such a protective coach of his players. I don't think he would ever say players were not ready (to take a penalty)."
Former England full-back Stuart Pearce disagreed with Mourinho, however.
"When we won the last two penalty shoot-outs before last night nobody was complaining about the process in picking the players to take them," Pearce added.
"Jadon (Sancho), Marcus (Rashford) and Bukayo look like strong characters. These three boys will spring back. Our profession is tough at times but you have got to be resilient."
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