Kane damaged ankle ligaments in early April and did not play until the Champions League final last Saturday, when he was off the pace as Tottenham Hotspur lost to Liverpool.
England manager Gareth Southgate elected not to start any of the seven players who contested the Madrid final meaning Liverpool captain Jordan Henderson is another among the substitutes.
With Kane on the bench, Manchester City winger Sterling has been given the honour of the captain's armband to mark his 50th England cap.
The winner of the tie meets hosts Portugal in Sunday's final in Porto with the loser fighting Switzerland for third place in Guimaraes.
England manager Gareth Southgate elected not to start any of the seven players who contested the Madrid final meaning Liverpool captain Jordan Henderson is another among the substitutes.
With Kane on the bench, Manchester City winger Sterling has been given the honour of the captain's armband to mark his 50th England cap.
The winner of the tie meets hosts Portugal in Sunday's final in Porto with the loser fighting Switzerland for third place in Guimaraes.