Around 1,500 people who won tickets via a ballot are expected to watch the game on a big screen in nearby Trafalgar Square, where scenes of utter jubilation unfolded after England's semi-final win Wednesday against Denmark.
The team -- nicknamed the Three Lions -- have not won a major competition since the 1966 World Cup, and ending the 55-year wait would represent a cathartic moment for the nation.
"Obviously they've been a bit unfortunate in the last 50-odd years, so I feel like this is their time to shine," said Luke Benton.
"I don't think there's a better time as well," added pal Cameron Morgan, as the pair took in the carnival-like scenes in central London.
"Everyone's been on house arrest for the last year or so... if there's a time, this is it!"
'What you dream of'
In a sign of the enormity of the occasion for expectant England fans, many began converging on fan zones and pubs, bars, restaurants and clubs in towns and cities across the country early Sunday morning.
Pictures posted on social media showed long lines of people queuing to get into pubs from south London to Northern England.
Wembley Way was clogged by early afternoon, with high-spirited supporters dancing in the streets, climbing up poles and setting off fireworks.
Mark Bennett, 40, who owns a restaurant in southwest England, was there with his son after forking out £2,700 ($3,800, 3,120 euros) on two tickets for the historic game.
"I want my son to experience the atmosphere... it was not something I wanted to miss," he told AFP, confiding his son would be missing school Monday.
"It would mean everything to me, it's what you dream of," he added of an England victory. "This is the biggest day I will ever have in football."
Eugenio Copelli, 63, a railway worker from north London, was one of the outnumbered Italian fans to make the pilgrimage to Wembley to soak up the atmosphere.
"I'm not nervous today because I do believe we are going to win it. It is going back to Rome," he told AFP.
Copelli had not bagged a ticket and would instead be watching with friends on a big screen elsewhere.
"We will be drowning our sorrows in coffee or drinking champagne," he added.
An England victory would be particularly special for Wembley-raised George Gristwood, who celebrates his 91st birthday Monday and remembers the team's only other final appearance in 1966.
"I've been to more England international matches than any England supporter. I've never missed a match," he said.
"The FA (English football's governing body) says they don't know anyone older than me that still goes (to games)," Gristwood added, noting he had visited at least 18 countries -- spanning most of Europe -- following the team.
Fellow persioner David Durant, 74, vowed to enjoy some celebratory beers if England won on home soil once again.
"This will be almost as good as that (1966). It's going to be a fantastic night if England win."
However, concerns about a rise in coronavirus infections and disruption to life around the stadium have irked some local residents not so hooked by the football.
"I'm happy it will be over soon!" said housewife Anna Bodo, 29, who lives a five-minute walk away with her two-year-old daughter.