The competition is comprised of four leagues, each split into four groups of three or four teams, and will replace the majority of international friendlies.
The Nations League, which has promotion and relegation, is designed to allow teams to play against those who are similarly ranked and will offer some who do not qualify for Euro 2020 via the normal route a path to the play-offs.
Scotland, who are still without a new manager, were one of the top seeds in League C, and were drawn into a three-team Group One.
Wales and the Republic of Ireland have been drawn together in Group Four of League B, alongside Denmark.
Northern Ireland will face Austria and Bosnia and Herzegovina in League B’s Group Three.
France, Germany and Netherlands make up Group One in League A.
The first round of matches for the 2018/2019 season will start in September and finish in November. Fixtures will be played at both home and away.
Group winners in League A will play a Final Four mini-tournament in June 2019 to decide the Nations League champion.
The full draw:
Group One: Germany, France, Netherlands
Group Two: Belgium, Switzerland, Iceland
Group Three: Portugal, Italy, Poland
Group Four: Spain, England, Croatia
Group One: Slovakia, Czech Republic, Ukraine
Group Two: Russia, Sweden, Turkey
Group Three: Austria, Bosnia and Herzegovina, Northern Ireland
Group Four: Wales, Ireland, Denmark
Group One: Scotland, Albania, Israel
Group Two: Hungary, Greece, Finland, Estonia
Group Three: Slovenia, Norway, Bulgaria, Cyprus
Group Four: Romania, Serbia, Montenegro, Lithuania
Group One: Georgia, Latvia, Kazakhstan, Andorra
Group Two: Belarus, Luxembourg, Moldova, San Marino
Group Three: Azerbaijan, Faroe Islands, Malta, Kosovo
Group Four: Macedonia, Armenia, Liechtenstein, Gibraltar