The arrests were made in Scotland by officers investigating football-related disorder.
Supporters from both sides were involved in a fight in Maiden Lane, Covent Garden, after England beat Scotland 3-2 on August 14.
The Metropolitan Police arrested two men aged 25 and 26 from Glasgow and two men aged 19 and 27 from Dundee.
A 21-year-old from Bonnybridge, Falkirk, was also arrested as part of Operation Arrowtip on Wednesday and Thursday. All five have been bailed.
Superintendent Andy Barnes, who leads Operation Arrowtip, said: "Violence amongst supporters has no place in football, be it before, during or after a match.
"The vast majority of supporters which attended last year's England vs Scotland match behaved in the right spirit and this was an isolated incident.
"These arrests show that anyone who chooses to engage in violence will be pursued by officers and arrested."
Thousands of Scotland supporters travelled to London for the fixture at Wembley Stadium, the first time the two sides had met since 1999.
There were two arrests at the match - one for drunk and disorderly behaviour and the other for public disorder.