England will not be involved after topping their group.
The Three Lions, who were semi-finalists in the competition during its debut year, thrashed Ireland 5-0 to earn promotion from League B.
The Boys in Green, who were already confirmed to finish third ahead of their Wembley defeat, could now face further misery in the playoffs.
Heimir Hallgrímsson's Ireland could drop down to League C with another defeat, with Scotland also bidding to avoid relegation.
Andy Robertson rescued the Tartan Army from finishing last in their League A group with a stoppage-time goal in a 2-1 win over Poland.
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Nations League draw: How to follow
The draw for the play-offs will be held on Friday, November 22.
The balls will be drawn at the House of European Football in Nyon, Switzerland at around 11:30am UK time.
It will be live-streamed for free on UEFA's website, with the best of the reaction available on talkSPORT.com.
Nations League draw: How does it work?
League A's third-placed teams will battle League B runners-up to determine which side either gets relegated or promoted at the expense of the other.
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This trickle-down method then applies to third-placed teams of League B and League C runners-up and continues to League D.
The Nations League play-offs will be two-legged ties for home-and-away games across the March international break.
Nations League draw: Play-off pots
There will be four games held in each bracket with the matches taking place over two legs.
The first legs will be held on Thursday, March 20 with the return matches then held on Sunday, March 23
League A vs League B
League A third place (Pot 1): Scotland, Belgium, Hungary, Serbia
League B second place (Pot 2): Greece, Austria, Turkey, Ukraine
League B vs League C
League B third place (Pot 1): Slovenia, Georgia, Iceland, Republic of Ireland
League C second place (Pot 2): Slovakia, Kosovo, Bulgaria, Armenia
League C vs League D
League C fourth place (Pot 1): Latvia, Luxembourg
League D second place (Pot 2): Malta, Gibraltar
Nations League draw: What about the quarter-finals?
The knockout draw for the remaining eight teams who are in with a chance of winning the trophy will proceed the one for the promotion/relegation play-offs.
It is set to get underway at 11am UK time.
It will include defending champions and Euro winners Spain - who will be hoping to retain their title against some European heavyweights.
France and Portugal are both seeking their second Nations League title as well, with Germany and the Netherlands also in the mix.
Group winners from League A will be seeded for the draw, and will each take on a side that finished runners-up.
The only condition is that teams that qualified from the same group cannot be drawn against each other, e.g. Germany and Netherlands.
League A Group winners (Pot 1)
Portugal
France
Germany
Spain
League A Runners-up (Pot 2)
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Croatia
Italy
Netherlands
Denmark
The quarter-final ties will also be held on March 20 and March 23 before the 2025 UEFA Nations League Finals are held in June.