Wayne Rooney, still technically the team captain, missed out on the squad after a season-long struggle for form and fitness for Manchester United, handing Kane the opportunity to become the latest man to take on the armband.
Jordan Henderson and Joe Hart have both previously captained their country under Gareth Southgate and the manager confirmed that he intends to keep mixing it up.
For Kane it marks a fitting end to a wonderful season, having cemented himself as one of the world's top strikers with a tally of 29 Premier League goals, enough for the league's Golden Boot.
And now he will be keen to add to his five-goal England haul as the Three Lions head to Hampden Park hoping to remain at least four points clear of second-placed Slovakia in Group F.
"Harry Kane will captain the side on Saturday," Southgate told a media conference. "I've shared the leadership around and I think that's important. People have said there's a lack of leaders but I don't see that to be the case.
"I felt it was important to give people the opportunity to lead in different ways. Everyone is different and has different styles, in training, in games, around the hotel and in meetings. Harry's one of a number of people I could have given the opportunity to.
"He was pretty chuffed. It's a great honour for a player and their family. The significance wasn't lost on him.
"It's a good moment for him. He's finished the season really well. We know his mentality and that he wants to be one of the best in the world.
"Harry has always had great belief in himself. When he worked with us in the Under-21s for the first time, he wasn't in Tottenham's team but he had great self-belief even then.
"We've got a team at the moment who aren't where they want to be individually or as a collective but they've got great potential and we're starting to tap into that. There's a long way to go but there's room for improvement for all of them.
"It's exciting, because they've got hunger and desire. They want to do well for their country and they're a great group to work with."
Time for a look around! pic.twitter.com/E9AJUKvg7j— England (@England) June 9, 2017
Liverpool midfielder Adam Lallana echoed Southgate's praise of Kane.
"Absolutely delighted for Harry," Lallana said. "I think this season he's demonstrated once again why he's one of the best players in the world.
"His form towards the end of the season was that of one of the best players in the world.
"He's still young and still has a lot of learning to do. If I'm selected it'll be a great honour to walk out behind him.
"The boss wants leaders in the group. I feel like I'm a leader and there's a lot of leaders. We need to develop more and the younger the better."