The EURO 2020 last-16 round will start with Wales-Denmark and Italy-Austria games on Saturday.
Wales will face Denmark in Amsterdam's Johan Cruijff Arena, while Italy will play against Austria in London's Wembley Stadium.
England, who topped Group D with 7 points, will meet Germany in a huge last-16 clash in front of nearly 40,000 fans at Wembley on Tuesday after the latter finished second in Group F, the so-called group of death.
In Wednesday's thrilling game, Germany salvaged a 2-2 draw against Hungary at Football Arena Munich with four points, behind France.
The Three Lions claimed a 1-0 victory over the Czech Republic on Tuesday evening.
Their most recent tournament meeting was at the 2010 World Cup that took place in South Africa when Germany clinched a 4-1 victory.
Round of 16 fixtures:
Saturday
Wales vs. Denmark, Amsterdam (1600 GMT)
Italy vs. Austria, Wembley (1900 GMT)
Sunday
Netherlands vs. Czech Republic, Budapest (1600 GMT)
Belgium vs. Portugal, Seville (1900 GMT)
Monday
Croatia vs. Spain, Copenhagen (1600 GMT)
France vs. Switzerland, Bucharest (1900 GMT)
Tuesday
England vs. Germany, Wembley (1600 GMT)
Sweden vs. Ukraine, Glasgow (1900 GMT)