The goalkeeper scored the Three Lions’ fifth successful kick before taking up his usual place between the sticks to save Josip Drmic’s effort, as England triumphed following a goalless draw in Portugal.
It gave Gareth Southgate’s team the bronze medal in the inaugural Nations League, having fallen short in Thursday’s semi-final against the Netherlands.
And Pickford said after the match that the team – who also reached the last four of the World Cup in Russia last summer – are ready to go one step further at next year’s European Championship finals.
“I wasn’t bad at school,” he said after successfully converting the first penalty of his career. “There’s a first time for everything. I’m just glad that I put it away so I don’t get battered on Twitter.
“We need to practice them. If you practice you might get your shout to take. The manager put me at number five. I had a little nervous moment when he said that, but I stepped up and put it away.
“We’ve been in camp for nearly three weeks. Daily we practice them. Sometimes with the ‘keepers, sometimes without them. Tom and Jack are sometimes arguing. But they go in goal at the end of the sessions. It’s hard work but it’s a team effort.
“He [Southgate] just came up to em after extra time. He came up and went ‘number five’, I went no problem. I tried to save a couple beforehand so I wouldn’t have to take one.”
England lost out 3-1 after extra time to the Dutch in the semi-final when a late goal from Jesse Lingard was ruled out after a VAR review.
Mistakes from John Stones and Ross Barkley in the extra 30 minutes let in the Netherlands to clinch victory and leave Southgate’s side facing up to another last-four exit.
“We’re still learning that process [VAR],” said Pickford. “We’ve got to be a bit more clever. Togetherness, key. Togetherness to bounce back from Thursday.
“We’re always learning. It’s about us now being able to take it to the next step. Reach a final and get some silverwear for the nation.”