Reigning Nations League champions Spain will play the Netherlands in the quarter-finals while former tournament winners France take on Croatia after the draw for the knockout stage was held in Nyon on Friday.
Germany were drawn against Italy while Portugal, who were winners of the inaugural edition of the Nations League, will face Denmark.
While the quarter-finals will be played over two legs home and away in March, the semi-finals are single legs which will take place in June, with the third-place playoff and final to be played three days later.
European champions Spain, Portugal and Germany topped their groups without losing a game to go into the seeded teams' pot along with France.
Spain have not played the Netherlands since a friendly match in November 2020. In their last competitive game, the Dutch thrashed the then-reigning world champions 5-1 at the 2014 World Cup.
The winners of that game will play either Croatia or France in the semi-finals. France and Croatia have played each other four times in the Nations League.
Portugal are also looking to win a second title and they still have Cristiano Ronaldo going strong. Ronaldo, who will be 40 when the knockout stage begins, leads the goal scoring charts in League A with five goals.
Only Sweden's Viktor Gyokeres (nine goals in League C), Norway's Erling Haaland (seven goals in League B) and Romanian midfielder Razvan Marin (six goals in League C) have scored more than Ronaldo in the 2024-25 tournament.
In the previous edition of the Nations League, only the top team from each group qualified for the knockout stage and went straight through to the semi-finals.
Nations League knockout fixtures
Quarter-final 1: The Netherlands v Spain
Quarter-final 2: Croatia v France
Quarter-final 3: Denmark v Portugal
Quarter-final 4: Italy v Germany
Semi-final 1: Winner of QF4 v Winner of QF3
Semi-final 2: Winner of QF1 v Winner of QF2
Quarter-final first leg: March 20
Quarter-final second leg: March 23
Semi-finals: June 4-5
Third-place playoff: June 8.
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