England will start their Nations League League B campaign away to the Republic of Ireland, while Scotland will host Poland in their League A opener.
The match in Dublin will take place on Saturday, 7 September at 17:00 BST.
Scotland’s opener at Hampden Park is scheduled for Thursday, 5 September at 19:45, the same time Northern Ireland will play Luxembourg at home in their first League C fixture.
Wales host Turkey in their League B opener on Friday, September 6 at 19:45.
England will host the Republic in their final group game on 17 November, with Finland and Greece completing the group.
They will be the first competitive fixtures between the Republic and England since a Euro 92 qualifier at Wembley in 1991. The most recent meeting between the two sides was a friendly in 2020, which England won 3-0.
Scotland, who won Group B1 last time to earn promotion to the top Nations League tier for the first time, also face Portugal and Croatia in League A1.
Steve Clarke’s side will travel to Portugal for their first away game on 8 September, with their final game away at Poland on 18 November.
Wales’ first away game is against Montenegro on 9 September, with their final game at home to Iceland on 19 November.
After opening their campaign against Luxembourg, Northern Ireland then travel to Bulgaria on 8 September.
Their away game against Belarus, scheduled for 12 October, is set to be played at a neutral venue.
European governing body Uefa has ordered all Belarusian clubs and national teams play home matches in its competitions at a neutral ground since March 2022 because of the country’s support of Russia’s military invasion of Ukraine.
Northern Ireland’s final fixture is away at Luxembourg on 18 November.
League A quarter-finals and promotion/relegation play-offs take place in March 2025, before single-leg semi-finals and a final in June 2025.
Spain are the trophy holders, having beaten Croatia on penalties in the final last June.
Nations League 2024-25 fixtures
(Kick-off 19:45 unless stated)
England – League B2
7 September: Republic of Ireland v England (17:00)
10 September: England v Finland
10 October: England v Greece
13 October: Finland v England
14 November: Greece v England
17 November: England v Republic of Ireland (17:00)
Scotland – League A1
5 September: Scotland v Poland
8 September: Portugal v Scotland
12 October: Croatia v Scotland (17:00)
15 October: Scotland v Portugal
15 November: Scotland v Croatia
18 November: Poland v Scotland
Wales – League B4
6 September: Wales v Turkey
9 September: Montenegro v Wales
11 October: Iceland v Wales
14 October: Wales v Montenegro
16 November: Turkey v Wales (17:00)
19 November: Wales v Iceland
Northern Ireland – League C3
5 September: Northern Ireland v Luxembourg
8 September: Bulgaria v Northern Ireland (17:00)
12 October: Belarus v Northern Ireland
15 October: Northern Ireland v Bulgaria
15 November: Northern Ireland v Belarus
18 November: Luxembourg v Northern Ireland