Spain, who beat England in the final of Euro 2024, won the Nations League in 2023 and lost last year's final, on penalties, to Portugal.
They will come up against Thomas Tuchel's England side in Group A3, with the Czech Republic and beaten 2023 finalists Croatia completing the section.
The Nations League will be the focus for European international football for the year after the 2026 World Cup, before attention switches to Euro 2028 qualifying.
Group matches, with everyone playing each other home and away, will take place between September and November this year.
The top two in each of the four groups in League A will advance to the quarter-finals in March 2027, the winners of which will progress to the four-team finals in June that year - likely to be hosted by one of the participating teams.
Reigning Nations League champions Portugal, who also won the inaugural edition in 2019, are in Group A4 with Denmark, Norway and Wales.
France, winners in 2021 and semi-finalists last year, will take on Italy, Belgium and Turkey in Group A1. Germany, the Netherlands, Serbia and Greece make up Group A2.
Draw for the 2026/27 UEFA Nations League, held in Brussels on Thursday:
Group A1: France, Italy, Belgium, Turkey
Group A2: Germany, Netherlands, Serbia, Greece
Group A3: Spain, Croatia, England, Czech Republic
Group A4: Portugal, Denmark, Norway, Wales
Group B1: Scotland, Switzerland, Slovenia, North Macedonia
Group B2: Hungary, Ukraine, Georgia, Northern Ireland
Group B3: Israel, Austria, Republic of Ireland, Kosovo
Group B4: Poland, Bosnia and Herzegovina, Romania, Sweden
Group C1: Albania, Finland, Belarus, San Marino
Group C2: Montenegro, Armenia, Cyprus, Latvia/Gibraltar
Group C3: Kazakhstan, Slovakia, Faroe Islands, Moldova
Group C4: Iceland, Bulgaria, Estonia, Luxembourg/Malta
Group D1: Gibraltar/Latvia, Malta/Luxembourg, Andorra
Group D2: Lithuania, Azerbaijan, Liechtenstein
- Latvia v Gibraltar and Luxembourg v Malta meet in two-legged play-off ties in March 2026 to decide their leagues.