Kane endured a lacklustre group stage before coming to life in the knockout stages of the tournament.
The Tottenham Hotspur striker has four goals to his name, leaving him in with a shout for the Golden Boot when Gareth Southgate's men take on the Azzurri in Monday's (AEST) final at Wembley.
If Kane is to follow up scooping the same prize at the 2018 FIFA World Cup, he will have to get the better of Chiellini and long-time ally Leonardo Bonucci at the heart of a formidable Italy backline.
Italy had amassed 11 consecutive clean sheets before a 2-1 Round of 16 win against Austria, and such solidity is a huge factor in the 33-match unbeaten run that has left it within touching distance of a first European title since 1968.
Thirty-six--year-old Chiellini recalled his maiden encounter with Kane in 2015 – an international friendly drawn 1-1 in Turin that was a second cap for a striker who now has 60 senior international appearances and 38 goals to his name.
"He's very technical, he shoots well from distance, he's good in the air, he takes free-kicks. He's a player who really impressed me right from day one," the defender explained, before recalling several discussions about Kane with Fabio Paratici, Juventus's former sporting director, who recently took on the same role at Spurs.
"I played against him during his time with Tottenham and I am a really big fan of him.
"You can ask Fabio Paratici, he’ll confirm that because we spoke about Kane so much over the past few years.
"Now Fabio Paratici will have the opportunity to work with him at Tottenham and I'll have the 'good fortune' to come up against him tomorrow night.
"It's always nice to play strikers such as these. It will be a tough battle but an exciting one."
A possible ploy for England would be for Kane to drop off the front and use his ability to thread throughballs for Raheem Sterling, who has scored three goals and provided an assist during a superb individual tournament.
"Everyone has their own attributes. If I try to match him in a footrace, me against Sterling, I don't think I'd ever beat him to the punch," Chiellini said.
"But maybe in situations where there's a ball to be won and it's a slightly more physical 50-50, or a long ball forward from the goalkeeper, I might be more likely to win the header. I need to try and limit their attributes.
"It almost makes me laugh because I think England's bench could have made it to the final on its own because it has some extraordinary players.
"We are going to try to limit their characteristics where we can, but thankfully it's not an individual game, it's a team game.
"It's not necessarily important whether Bonucci and Chiellini can stop Sterling and Kane; it's about whether Italy will beat England."
A noted no-nonsense defensive hard man over the course of his career, Chiellini has adopted a demeanour throughout UEFA Euro 2020 that has been at once jovial and somewhat terrifying, perhaps in line with the pre-tournament prescription he repeated on Sunday (AEST) of Italy needing "just that hint of madness and cool heads".
He reacted with delight when a Kevin De Bruyne piledriver stuck him during the 2-1 quarter-final win over Belgium, while his playful jostling with Spain captain Jordi Alba before the semi-final penalty shootout was instant meme material.
"I really am savouring every last drop of my career. I've always got a smile on my face and I always try to have the utmost respect for my opponents," Chiellini said.
"I'm trying to hug them, smile, have a bit of a laugh. That's something I've always done and in these games I really am trying to enjoy every single moment, even more than I did in previous years."
On the Alba incident, Chiellini added: "No, it wasn't mind games by any means. That's how I am in good times and bad. My team-mates love me and there might be times when opponents like me less.
"After all these years, I think there is mutual respect between me and my opponents."