The fixture, to help celebrate the Football Association's 150th anniversary year, is the first time the two countries will have met in 14 years.
Brown captained Celtic to the last-16 of the Champions League last season where they were knocked out by Italian giants Juventus but the midfielder claims that leading Gordon Strachan's side out in front of around 25,000 of the Tartan Army will eclipse even that honour.
"It is going to be a great occasion taking the lads out at Wembley," Brown said. "It is going to be huge, it is definitely right up there, even bigger than taking Celtic out for the last-16 of the Champions League.
"It is going to be hard, high-tempo and a great occasion for the fans as well and I'm sure the Tartan Army will be there in their thousands.
"I think there is a lot more pressure on them to beat us. We are the underdogs. But we have got great players and match winners as well so we are all looking forward to it."
Scotland forward Don Hutchison scored the only goal of the game with a header when the two countries met in London in 1999 although the Scots lost their Euro 2000 play-off qualifier 2-1 on aggregate.
However, Brown remembers what is still remembered as a famous Wembley win.
"I was 14 the last time they played and it was a great goal by Don Hutchison, a header," he said. "It was just a great occasion for every Scotland fan and everyone in Scotland.
"There is no greater feeling than to play against England, especially as a Scotland player and a Scotland fan. I am really looking forward to the game."