Supporters sporting replica kits, patriotic face paint and fancy dress began swarming around the historic stadium eight hours before kick-off, eager to soak up the atmosphere ahead of the semi-final.
Victory would secure the England men’s team’s first appearance in the final of a major football tournament since their 1966 World Cup win.
And fans were confident of overcoming underdogs Denmark in front of a partisan 60,0000 crowd, where England supporters will outnumber the Danes by around six-to-one.
Three England fans dressed as lions said they were watching the match at Wembley Stadium with a fourth fan dressed as their “lion tamer” who would “keep us under control if Denmark win”.
Ben Edwards, 43, Craig Pope, 47, Matt Glew, 38 and “tamer” Laurence Page, 72, who was wearing an England flag top hat, from Maidstone, said they were confident of victory.
Mr Glew told the PA news agency: “It’s our toughest test yet but I reckon we’re going to win 2-0.”
Pointing at his lion headgear, the former banker added: “We paid about £100 per hat but it was worth every single penny, we’ve been asked for autographs and all sorts.”
Mr Edwards, who works in cyber security, said: “Denmark aren’t going to win – it’s coming home.”
Mr Pope, who works in construction, added: “We’re going to get past our semi-final hoodoo.”
Jo Andrews, 36, a property manager from Portsmouth who was wearing an England hat and face paint, said she was “absolutely excited” to be there.
She said: “We are definitely going to win tonight – 3-1.
“This is our turn, this is our chance and we are going to win tonight and we are coming back Sunday.”
The Duke of Cambridge, who is president of the Football Association, will be among those inside the ground to watch the match – the first time the men’s team has made it to the semi-final of a European Championship since an ill-fated penalty shootout defeat to Germany at Euro 96.
The British Beer and Pub Association reckoned thirsty punters would buy nearly 10 million pints during the course of Wednesday in venues across the country, with 6.8 million of them in a two-hour period around the match itself.
Elsewhere, England fans without tickets for the official fan zone in central London’s Trafalgar Square gathered in the area to avoid “missing out” on the atmosphere.
Luke Hughes, 19, a student from Watford, said: “I’ve seen the scenes on social media of everyone chanting and singing in London after the game has finished – there is no way I am missing that.
“I think it will be a tough game, maybe decided on one goal, but if we win, this place will be electric. It’s coming home.”
Optimistic England fan Benjamin Crew, 32, a roofer from Woking in Surrey, said: “I’m feeling fantastic, we’re going to win the lot.”
Speaking from Boxpark in Croydon, he added: “I think England will win 7-0 tonight.”
And Wycombe Wanderers striker Adebayo Akinfenwa who was also at Boxpark Croydon, said he was not worried about “the old taboo” of a penalty shootout.
He told PA: “I’m confident about the semi-final but I don’t want to overthink it.
“It’s a new generation and I don’t think they have the old taboo on their shoulders.
“I think they’re young, they’re fearless, and they’ll see out the job.
“We’re winning the game.”
Police urged those watching the match in pubs and fan zones to respect social distancing, while an estimated 20 million people are expected to watch the match on television.
England superfan Chris Dowse, who lives on the flag-bestrewn Kirby Estate in Bermondsey, south-east London, said he had declined the offer of tickets to the Euro 2020 semi-final because he would rather watch the game in the company of his neighbours.
The 42-year-old said: “I’ve been offered tickets but I’ve turned them down. Firstly, I’m not rich and I’d like to spend that money on my kids.
“But secondly, I am really proud of what we’ve achieved on this estate, so I will be watching it here.”
England were installed as clear favourites among bookmakers to beat Denmark, having progressed through the tournament without conceding a goal.
But the Danes emerged from heartbreak in their opening match defeat to Finland – when talisman Christian Eriksen collapsed on the pitch – to reach the last four.
They will be backed at Wembley by around 8,000 UK-based Danish supporters, with international travel restrictions effectively preventing supporters visiting from Denmark.
Even still, the 60,000 crowd represents the largest at a domestic sporting event since coronavirus rules were first introduced in spring last year, although Business Secretary Kwasi Kwarteng said he could not guarantee there will not be an outbreak of Covid-19 cases linked to football fans watching the game.
The winners will face Italy in the final, also at Wembley, at 8pm on Sunday.