The Three Lions roared at the Stadio Olimpico in Rome with a mesmeric performance against the Ukrainians.
It was a dream start for Gareth Southgate’s men when captain Kane broke the deadlock only four minutes into the game after receiving a sumptuous pass from Raheem Sterling.
Harry Maguire doubled England’s advantage with a thunderous header from Luke Shaw’s cross just a minute after the break.
Kane had his second on the night after a inch-perfect cross from Shaw on the 50th minute mark before substitute Jordan Henderson sealed England’s emphatic win with another header from Mason Mount’s corner on 63 minutes.
“What a great performance in a big game,” Kane said after the game.
"We were favourites, there was a lot of pressure and a lot of expectations. The performance was top-drawer. Another clean sheet, four goals, it was a perfect night for us.
"We're building on [clean sheets]. We have a great unit here from front to back. It's a vital part of winning games and tournaments.
"We've got a big semi-final coming up. We're on the right path.
"It's where we wanted to be. We set out a vision before the World Cup of what we want to achieve.
“We are knocking it off step by step. The World Cup was great but we fell short, we had a good run in the Nations League. We're in another semi-final.
"Now it's about getting over the line, the next step that we have got to do on Wednesday.
"We have more experience [than 2018]. We've been playing for our clubs in big games - Champions League finals, Premier League title races. We're looking confident. Hopefully we can continue that.
"The job is not done yet. There's a lot more football to play.
"It's always nice to score early in a game. It's a great feeling to help the team. There was a lot of talk about me and my performances. But I'm just ready for the next game and try to lead this team to the European final."