The Tottenham striker will make his full international debut at the Juventus Stadium, having opened his England account within 79 seconds of coming off the bench against Lithuania on Friday.
As the sides prepare to meet for the first time since Italy's 2-1 win in the group stage of the World Cup last year, Rooney is well versed in the Italian style of defending.
"With Italian defenders, they're clever defenders. They do anything to try and stop you and you have to be aware of that and not be frustrated," he told British media outlets.
"I think it's a passionate country who love their football, probably the closest in Europe to South American teams. They'll do anything to stop you.
"They're tough to play against, organised, make it as difficult to play against as possible. They're the best in Europe at doing that."
Kane's strike in Friday's 4-0 win at Wembley was his 30th goal of the season in all competitions, with Rooney taken aback by the 21-year-old's form.
"I'm as excited as everyone in the country. He's had an unbelievable season," Rooney added.
"Going into the season there were questions whether he would start for Tottenham.
"At the minute, what Harry is doing he must continue doing. He's taking the ball and running at the defenders, getting shots at goal.
"That's all he has to do [on Tuesday]. I'm sure if he does that the way he has been, he'll be fine."
