The four countries were winners of their respective League A groups last year and compete in the mini-tournament in mid-year to decide the 2022/23 title.
Wednesday's draw, conducted at UEFA headquarters in Switzerland, has the Netherlands hosting Croatia, fresh from reaching the World Cup semi-finals in Qatar, in Rotterdam on June 14 with Italy and Spain clashing in Enschede the next day.
The winners advance to the final in Rotterdam on June 18, with the third-place playoff earlier the same day in Enschede.
Spain were runners-up to France in the last edition in 2021, first eliminating hosts Italy in their semi-final with a Ferran Torres double in a 2-1 victory in Milan.
Italy and the Netherlands also return for a second appearance at the finals while this is Croatia’s first time.
The Italians were third in 2021 while the Dutch runners-up in the inaugural event in Portugal in 2019.
The Nations League is a biennial competition contested by all European countries, which are divided into a four-tier league structure. It has effectively replaced friendly matches previously played on dates on the international match calendar.
June 14: Netherlands v Croatia, Rotterdam
June 15: Spain v Italy, Enschede
Third place play-off:
June 18 in Enschede
June 18 in Rotterdam