The 21-year-old had never previously been called up to the senior team, but a string of impressive performances in the Premier League have caught the eye of manager Roy Hodgson.
Kane is currently the top-scoring Englishman in the top flight, having scored one more goal that QPR's Charlie Austin.
The forward - who has 16 goals to his name - is third overall, with only Diego Costa of Chelsea and Manchester City's Sergio Aguero having netted more.
Kane has scored eight goals in 10 appearances for England's Under-21 side and is the only uncapped player selected, with other in-form strikers such as Austin and and Burnley's Danny Ings overlooked by Hodgson.
An knee injury to Ben Foster sees Joe Hart and Fraser Forster selected as the only two goalkeepers, while Liverpool's Daniel Sturridge could make just his second appearance since the World Cup having struggled with a thigh problem.
Squad in full:
Goalkeepers: Fraser Forster (Southampton), Joe Hart (Manchester City)
Defenders: Leighton Baines (Everton), Gary Cahill (Chelsea), Nathaniel Clyne (Southampton), Kieran Gibbs (Arsenal), Phil Jagielka (Everton), Phil Jones (Manchester United), Luke Shaw (Manchester United), Chris Smalling (Manchester United), Kyle Walker (Tottenham).
Midfielders: Ross Barkley (Everton), Michael Carrick (Manchester United), Fabian Delph (Aston Villa), Jordan Henderson (Liverpool), Adam Lallana (Liverpool), James Milner (Manchester City), Raheem Sterling (Liverpool), Andros Townsend (Tottenham), Theo Walcott (Arsenal).
Forwards: Harry Kane (Tottenham), Wayne Rooney (Manchester United), Daniel Sturridge (Liverpool), Danny Welbeck (Arsenal).
