Spain crushed Germany on Tuesday with a commanding 6-0 victory to secure a spot in the Nations League final four.
Ferran Torres scored a hat-trick and Alvaro Morata, Rodri and Mikel Oyarzabal also starred in Spain's triumph.
Germany only needed a draw to top the Group A4 standings, but were completely overpowered by the Spaniards, who led the scoring by three goals before half-time.
The other group fixture between Switzerland and Ukraine was cancelled after a coronavirus outbreak on the Ukrainian side.
In Group A3, Olivier Giroud scored a brace, and Benjamin Pavard and Kingsley Coman also hit the net as France beat Sweden 4-2. Didier Deschamps' side had already secured a place in the Nations League finals on Saturday after beating Portugal.
Cristiano Ronaldo and his teammates beat Croatia 3-2. Sweden finished last in the group and were relegated to the competition's League B.
Biggest since 1931
Germany suffered their biggest defeat since 1931 on the same day Manuel Neuer became the most capped goalkeeper in the national team with 96 games, surpassing Sepp Maier's record (95).
"This is very disappointing to all of us," Manuel Neuer told the broadcaster ARD.
"I’m part of the team. We messed up the game together. The body language and the communication were too little. We should have talked more, right after the first goal."
Germany coach Joachim Loew said the defeat was "difficult to explain. Everything went wrong." His side had only two shots on goal (compared to Spain's 23) and the first one only arrived in the 76th minute.
"In the second half, we tried to play man against man, to press them, to score, and get back into the game. But Spain were playing better, being faster and more precise. We had no chance," Loew said.
Hat-trick scorer Torres celebrated the evening saying: "Every player dreams of scoring a hat-trick and to do it against Germany makes me very happy."
Team-mate Morata added he "can't wait to see" what people will say after the game.
"They sure tell us when we've not hit our levels. Today, however, nobody can even offer a 'but...' about this win."
France suffered an early setback against Sweden, but Giroud's brace, a goal by Pavard and a late effort by Coman secured a win in the last international break of the year.
"The manager spoke to us before the game and said that even though we were already qualified we needed to finish well as a team and that's what we did," France midfielder Moussa Sissoko said.
Sweden put on a brave performance after an impressive showing last time out against Croatia, but it came too late to prevent relegation.
Portugal also came from behind to clinch a 3-2 away victory at Croatia. But the win only served to close the year in good style as the Portuguese side could no longer reach the top of the standings.
"We finished the Nations League well, not as we wanted, but we gave a good answer," Portugal defender Nelson Semedo said.
Teammate Francisco Trincao added: "The important thing was to win, we wanted to give a good answer to Saturday's defeat."
Croatia avoided relegation, but only thanks to Sweden's defeat at France.
"We achieved our goal, which was to remain in the top league. Unfortunately, it was not because of our good games or results, but things went to our favour at the end," coach Zlatko Dalic.
In Group C1 Luxembourg drew 0-0 with Azerbaijan, while Montenegro secured promotion to League B by beating bottom-of-the-group Cyprus 4-0.
Latvia clinched their first-ever win in the Nations League with a 5-0 triumph against bottom-of-the-group Andorra in D1, and Malta drew 1-1 with promoted Faroe Islands.
Gibraltar and Liechtenstein also drew 1-1 in D2 as the hosts clinched a spot in League C.