England was riding the crest of a wave after beating Germany in the Round of 16 and, in its first game away from Wembley this tournament, took the lead inside four minutes when Raheem Sterling played Kane in to score.
That was England's earliest European championship goal since Michael Owen's against Portugal in 2004 and the Three Lions added two more quick-fire goals to the tally in the first five minutes of the second half through Harry Maguire and Kane once again.
Substitute Jordan Henderson's first international goal gave Gareth Southgate further reason to cheer as his side kept its fifth clean sheet in a row from the start of the tournament, something only Italy has previously managed at a FIFA World Cup or European championship.
Sterling and Kane scored in England's Round of 16 win against Germany and the pair combined for its side's early opener in Rome, the Manchester City winger threading the ball through for his team-mate to poke past Georgi Bushchan.
England had failed to win any of the previous five European championship games in which it had scored in the opening four minutes and was given a warning when Jordan Pickford was tested by a Roman Yaremchuk strike.
England continued to dominate possession but ist only other attempt on target in the first half came via a powerful Declan Rice drive which was batted away by Bushchan.
Ukraine was making just its second quarter-final appearance at a major tournament and ended the opening period on top, though found itself further behind 55 seconds into the second half when Maguire headed home from a set-piece, awarded after Kane was needlessly fouled.
Luke Shaw set up that goal and also played in the cross that Kane headed through the legs of Bushchan for England's third, effectively killing off the contest with 40 minutes to play in the Italian capital.
England continued to search for goals and Henderson, just six minutes after replacing Rice, made the most of some terrible Ukraine defending to head in a fourth for Southgate's side, which had little trouble in seeing out the win.
"He can say whatever he likes, I just keep my head down, ignore everything. My main objective is to help England."— beIN SPORTS (@beINSPORTS_EN) July 3, 2021
Who is Luke Shaw talking about? #beINEURO2020 #EURO2020 #UKRENG
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"To score in two quarter-finals back to back it's a dream come true!" 😍— beIN SPORTS (@beINSPORTS_EN) July 3, 2021
Harry Maguire talks us through a memorable night in Rome for England. #beINEURO2020 #EURO2020 #UKRENG
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