It will be the first time in a quarter of a century that the two teams will come head-to-head in an international football tournament, after Scotland qualified for the Euros in November last year with a play-off victory in Serbia.
The Tartan Army continued to descend on London on Friday (18 June), hours before the 8pm kick-off.
One devoted member of the Army is Sir Rod Stewart, who is attending the game tonight to witness his beloved team vie for a win against their UK rivals.
But some are confused as to why the English-born singer is such a dedicated Scotland supporter.
So, why does Rod Stewart support Scotland?
Here is everything you need to know.
Why does Rod Stewart support Scotland?
The Da Ya Think I’m Sexy? singer was born in Highgate, North London, and also grew up in the UK’s capital.
But his father, Robert, was Scottish.
He lived in Scotland with his English wife, Elsie, and their first four children were born there.
However, the family moved to London, where their youngest son Rod, now 76, was subsequently welcomed to the world.
Despite his English upbringing, Sir Rod has previously explained that he grew up supporting Scotland, as well as Celtic.
And he has confirmed that his own sons are also Scotland football and rugby supporters and life-long Celtic fans.
Speaking to the Herald, Sir Rod said: “They are aware of the tartan blood inside them.”
Even though he’s one of the Tartan Army's most celebrated members, Sir Rod has revealed in the past that he does not consider himself Scottish.
In an interview to mark his 70th birthday in 2015, he said: “It does surprise me when people say to me, ‘I thought you were Scottish.’ I have never ever said I was Scottish.
“All I am is very proud of my father who was Scottish and the wee bit of Scottish blood I have in me. It’s a spiritual thing for me.”
What has he said about the Euro 2020 game against England?
When Scotland qualified for the Euros last year - the national team’s first major tournament since the 1998 World Cup - Sir Rod told BBC Breakfast he was “over the moon”.
But he admitted it would be an “uphill climb” for the squad to win against England at Wembley.
“I’ve been watching these games since I was 14, England and Scotland, and I’ve had my heart broken so many times.
“I’d love to see the Scots win. It is going to be an uphill climb, but win or lose, as long as they make us proud.”
Sir Rod called himself the “cockney Scotsman” and jokingly referred to the England side as “the old enemy”.
He added: “I’m actually going to be going, I’ve got a box for six, cost me an arm and a leg, I had to sell the house to buy it.
“I’m taking my two sons and three of my best friends who are all Scotland supporters, we are just going to hope for the best.”
And the singer also offered a prediction for the final score, saying: “One-nil to Scotland and I will die a happy man.”
Has Rod Stewart recorded any Scotland songs?
The rocker has also played his part in contributing to the national team’s music, recording versions of Que Sera Sera for Scotland’s 1978 World Cup campaign.
Perhaps more famously, he recorded his traditional song Purple Heather with the Scotland squad for Euro ‘96.
Sir Rod has hinted he would “love to” record another football anthem if he was asked.
He said on BBC Breakfast: “We don’t need a song right now because we’re already in the finals. But for the World Cup, if I was asked to do one, I’d love to do one.”