The Tottenham forward had scored 53 goals for the Three Lions before the trip to Naples, where Gareth Southgate’s side begun their Euro 2024 qualification campaign.
It was Kane’s first appearance in an England shirt since December at the World Cup against France, when he netted one penalty but missed another in a heartbreaking quarter-final defeat.
The 29-year-old had been tied with Rooney since then, but has now claimed the record outright – ironically, from 12 yards.
Kane netted his record-breaking goal from the penalty spot shortly before half-time, with Giovanni Di Lorenzo adjudged to have handled the ball inside the box after an intervention from VAR.
The skipper stepped up and fired the ball into the right side of the net, with goalkeeper Gianluigi Donnarumma diving the wrong way.
Kane looked overjoyed to finally bag the record outright, having been asked about it for well over a year as he closed in on the milestone, and was mobbed by his team-mates.
He managed to bag his 54th goal in just his 81st appearance for England, with Rooney having scored his 53 goals in 120 appearances.
Bobby Charlton (49 goals in 106 appearances), Gary Lineker (48 goals in 80 appearances) and Jimmy Greaves (44 goals in just 57 appearances ) complete the top five.
Kane – who has been in superb form this season, netting 21 times in the Premier League – will certainly fancy his chances of adding considerably to the record before he hangs up his boots.
Speaking to Channel 4 prior to breaking the record, Kane said: ‘I love playing for England, so to have that opportunity to do it this week would be great.’
Kane will have his sights set on eclipsing another of Rooney’s milestones this season, with the Spurs striker just four goals shy of the 37-year-old’s 208 Premier League strikes.
Although Kane is still someway short of all-time Premier League top scorer Alan Shearer on 260 goals, he is likely to take second place from ex-Everton and Manchester United forward Rooney before the season is over if he continues his current scoring rate.
MORE : Everything you need to know about England’s Euro 2024 qualifying campaign
MORE : Ben Foster baffled over Ben White’s England snub with Arsenal star not picked by Gareth Southgate
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