The 18-year-old Chelsea winger was promoted from the Under-21 squad on Monday as a replacement for injured Manchester United full-back Luke Shaw.
Hudson-Odoi is yet to start a Premier League game for the Blues and has not been capped at an age group above England Under-19s.
But he will take his place in manager Gareth Southgate’s ranks for the Euro 2020 qualification double-header against Czech Republic and Montenegro.
The Under-17 World Cup winner is the latest in a line of young talent given a chance to shine in Southgate’s senior squad and joins the likes of Jadon Sancho and fellow squad debutant Declan Rice in the latest squad.
Kane, having trained with Hudson-Odoi over the past two days, has been impressed by what he has seen so far and what he feels the precocious forward will bring.
“He has been great,” said the Tottenham Hotspur striker.
“He wants to take full advantage of his opportunities and it looked like he was enjoying it out there. We are excited to have him.
“Competition for places is huge at the moment, everyone is fighting for a spot and the youth aren’t scared to go and express themselves, try their skills and try to score a goal, and that is what we want.
“As an England team we want that flair and flexibility. It is a great sign in this country we are producing these type of players.”
Rice was included in the initial squad having been cleared by FIFA to change allegiances from the Republic of Ireland.
The West Ham midfielder picked up three friendly caps with the Republic before opting to represent England.
Kane, too, was eligible for both, but said his situation did not mirror that of the defensive midfielder with Rice’s decision played out in public.
“Mine was a bit different,” he said of his own possibility of playing for either England or the Republic of Ireland.
“My nan and granddad were Irish on my dad’s side. I had that decision, but it never really came about. As I started playing in the Premier League the England call-up didn’t come long after that.
“There were rumours, but I never said no to anyone. I don’t know if they spoke to my agent, but I always wanted to play for England and my dream was to play for England. Thankfully that worked out.
“I’m sure it was a tough one for him (Rice). He’s enjoying the season he has been having so far. He took the time with his family and close friends and the decision he made is one he thinks will be best for his future and no one can blame him for that.
“I can tell just by being with him for a couple of days he will give everything for his country.”
The flair and flexibility brought to the squad by the new faces is complemented by a sense of fearlessness, according to Kane.
Sancho, 18, scored a Panenka penalty in a training session shoot-out, leaving the Three Lions captain impressed.
“That shows no fear,” he said.
“We had a little sudden-death penalty shoot-out and he chipped his one down the middle, which takes a bit of bottle, especially at his age.
“He is enjoying it and that is what we want. We want people to express themselves in every part of the game and in training and he certainly did that.
“I wouldn’t do it for the rest of my career let alone at that age. He has been working in the last camps and looks like a player who wants to learn and improve, in finishing sessions or tactically.”