The trio will feature in Group One of League A, the top division of the four-tier tournament that UEFA has introduced to replace international friendlies and which will run alongside the traditional European championship qualifiers.
It was an early boost for the competition which critics say is too complex, adds to an already crowded calendar and, because it provides an additional path to tournaments such as Euro 2020, makes it too easy for the top teams to qualify.
UEFA, concerned that international football is losing popularity to the club game, argues that the league will provide the top nations with more competitive matches against each other.
In the other League A groups, Italy, who failed to qualify for this year's World Cup finals, will face European champions Portugal and Poland in Group Three while Spain take on England and Croatia in Group Four.
Belgium will meet Switzerland and Iceland in Group Two, arguably the easiest.
The Nations League features all 55 of Europe's national teams divided into four divisions -- Leagues A to D -- that are themselves split into four groups, to be played between September and November.
In League A, the winners of each group qualify for the semi-finals, which will be played in June 2019, followed by the final. The four last-placed teams are relegated to League B.
In the other leagues, the four group winners are promoted and last team in each group goes down.
Each league also has one place at Euro 2020, offering a back door for teams who do not qualify through the regular qualifiers.
This mechanism guarantees that one fourth-tier side -- such as Georgia, Azerbaijan, Faroe Islands or Malta -- will reach Euro 2020.
Germany coach Joachim Loew said the new competition was "really interesting."
"I like these kind of games," he told reporters. "France is a big nation, very good players, and Netherlands too, so it's interesting for us, our players and of course our fans. It's better than the friendly games we have sometimes.
"I'm really happy."
Poland coach Adam Nawalka agreed. "It's a very good idea to have this competition instead of friendlies, we have a very interesting group with the European champions Portugal and four-times world champions Italy," he told Reuters.
Portugal coach Fernando Santos told UEFA's website: "One of the positives with this competition is more games between teams of a similar standard.
"Some countries knew they will always struggle to get to a World Cup or a EURO, and they will now have another reason to invest in grassroots development and, of course, all European football will benefit from that."
(Writing by Brian Homewood; Editing by Christian Radnedge and David Goodman)
