Wembley Stadium will now host a total of seven games at Euro 2020 after UEFA dropped Brussels as a venue because of stadium problems.
The capital of Belgium has lost the right to be a host for the tournament because of delays in the construction of the 60,000-capacity Eurostadium project on the site of Heysel.
Wembley had originally been selected to host the semi-finals and final of the competition in 2014 and will now host an additional three group games and one last-16 fixture.
England's national stadium is one of 12 venues across Europe hosting Euro 2020 games.
Both the Principality Stadium of Wales and Sweden's Stockholm Friend's Arena had been hoping to replace Brussels, but UEFA opted against the venues for last season's Champions League and Europa League finals.
In response, the Football Association of Wales said in a statement: "The concept of taking UEFA EURO 2020 to 13 different countries was devised to allow smaller countries, like Wales, to have a unique opportunity of being involved in staging a major tournament. Wales has never staged a EURO or World Cup Final and this was its one and only chance of doing so.
"The FAW complied with all of the bid requirements and has written to UEFA to request feedback on the decision so that it can understand the reasons behind the vote for future reference. The FAW wishes the FA and Wembley Stadium the very best for UEFA EURO 2020, which is sure to be a fantastic tournament."