Southampton winger Nathan Redmond has also been rewarded with a call-up after strong domestic form, while Fabian Delph, Joe Gomez, Jesse Lingard and Harry Winks are all involved after missing the March internationals through injury.
Bournemouth striker Callum Wilson and West Ham midfielder Declan Rice keep their places, but there is still no room for highly rated Crystal Palace right-back Aaron Wan-Bissaka.
Southgate has confirmed that a reduced 23-man squad will be confirmed by Monday 27 May.
Full Provisional 27-Man England Squad for UEFA Nations League Finals:
Goalkeepers: Jack Butland (Stoke), Tom Heaton (Burnley), Jordan Pickford (Everton)
Defenders: Trent Alexander-Arnold (Liverpool), Ben Chilwell (Leicester), Joe Gomez (Liverpool), Michael Keane (Everton), Harry Maguire (Leicester), Danny Rose (Tottenham), John Stones (Man City), Kieran Trippier (Tottenham), Kyle Walker (Man City)
Midfielders: Dele Alli (Tottenham), Ross Barkley (Chelsea), Fabian Delph (Man City), Eric Dier (Tottenham), Jordan Henderson (Liverpool), Jesse Lingard (Man Utd), Declan Rice (West Ham), James Ward-Prowse (Southampton), Harry Winks (Tottenham)
Forwards: Harry Kane (Tottenham), Marcus Rashford (Man Utd), Nathan Redmond (Southampton), Jadon Sancho (Borussia Dortmund), Raheem Sterling (Man City), Callum Wilson (Bournemouth)
Having topped Group 4 of League A at the back end of last year, England qualified for the first ever Nations League finals alongside Netherlands, Switzerland and Portugal.
Southgate's team will face the resurgent Dutch in the second semi-final in Guimaraes on 6 June, 24 hours after Portugal and Switzerland meet in the first semi-final in Porto.
The two winners will then contest the final in Porto on 9 June for the chance to lift a trophy. For England, it would be the first senior international silverware since 1966.
England finished fourth at last summer's World Cup in Russia and are currently ranked fourth in the world by FIFA after the official list was most recently updated last month.