"Harry Kane will make full debut and play from the start and Wayne Rooney will captain the team," Hodgson told reporters.
"It's nice to see the two of them on the field together from the start. Harry certainly deserves his chance."
Kane, joint top scorer in the Premier League with 19 goals, headed England's fourth goal 80 seconds after replacing Rooney in the 4-0 win over Lithuania in Friday's Euro 2016 qualifier.
Rooney, who has 102 England caps and is on the verge of breaking Bobby Charlton's 45-year-old England scoring record of 49 goals, was delighted at the prospect of playing alongside Kane for the first time.
"It's exciting that Harry Kane has done well in the Premier League. It's fantastic. Hopefully he continues that form with England," said Rooney, who has scored 47 international goals..
"It's a big night for him with his first start for England. I'm sure he'll be excited. He'll go out and try and give his best and I'm excited to play with him and hopefully we can do well to try and help the team win.
"Our aim is to reach the Euros. Tomorrow will be a good test and we are looking forward to it."
Hodgson declined to follow Italy coach Antonio Conte's tactic in naming his final 11 on the eve of the match.
Instead, all he would say was: "It's a friendly match and it's a time to experiment with some of the players.
"We take the game very seriously and it's a great opportunity for players who haven't had the opportunity in some of the qualifiers to show that they really deserve their place in the squad.
"It's an opportunity for players to impress both managers."
England top Group E in their Euro 2016 qualifiers with 15 points from five matches while Italy are second on 11 points in Group H, two behind leaders Croatia.
(Writing by Pritha Sarkar in London, editing by Justin Palmer)
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