Shaw has impressed for United in the early stages of the 2018-19 campaign, and the left-back has been named in the 23-man squad ahead of teammate Ashley Young.
Shaw is one of five new faces from the squad that finished fourth at the 2018 World Cup, with Liverpool duo Joe Gomez and Adam Lallana, Burnley's James Tarkowski and Southampton goalkeeper Alex McCarthy also included.
England will open their UEFA Nations League campaign against Spain on September 8, before taking on Switzerland in a friendly on September 11.
Goalkeepers: Jack Butland, Jordan Pickford, Alex McCarthy
Defenders: Trent Alexander-Arnold, Joe Gomez, Harry Maguire, Danny Rose, Luke Shaw, James Tarkowski, John Stones, Kieran Trippier, Kyle Walker
Midfielders: Dele Ali, Eric Dier, Adam Lallana, Jesse Lingard, Ruben Loftus-Cheek, Jordan Henderson, Fabian Delph
Attackers: Marcus Rashford, Raheem Sterling, Danny Welbeck, Harry Kane