The 28-year-old striker both won and, following a lengthy VAR consultation, converted a late penalty that saw the Three Lions salvage a 1-1 draw at the Allianz Arena, having previously trailed to Jonas Hofmann's 50th-minute opener.
The milestone goal also saw Kane bring up his half century of goals for his country, thus becoming the only the second player ever to do so.
The Tottenham forward is now three goals behind his retired rival Rooney and has has a 49-cap buffer in which to usurp the international scoring record.
Now that Kane has sealed his initiation into England's illustrious and highly exclusive '50 Club,' we thought it timely to sift back through the striker's international goals and pick out a few of the very best in terms of technique, spectacle and grandeur.
After rattling in 29 goals for Tottenham, the 21-year-old Kane was called into the England squad for the first time by Roy Hodgson ahead of a Euro 2016 qualifier against Lithuania in March 2015.
The budding striker started on the bench but eventually emerged in the 71st minute when he came on to replace Rooney. He had to wait a full 79 seconds to open his international account, heading home at the far post with only his third touch of the night.
England rallied from two goals down to secure an impressive 3-2 comeback victory over the reigning World Champions with Kane's smart strike on the hour mark proving the catalyst.
Playing in a mask to protect an injured cheekbone, the Spurs striker swivelled on the edge of the box before driving a measured finish low beyond Manuel Neuer's outstretched arms.
Kane took the national team's armband for the first time against Scotland in a 2018 World Cup qualifier at Hampden Park and also managed to mark the occasion with a volleyed goal.
The two sides played out an entertaining 2-2 draw, with Kane rescuing a point for the visitors in the 93rd minute after the Scots had raced ahead by scoring twice in the final three minutes of regulation time.
Moment of the Day 👀— FIFA World Cup (@FIFAWorldCup) June 18, 2018
When @England's Harry Kane netted an injury-time winner on his #WorldCup debut 💪
🎥 Highlights 👉 https://t.co/LOdKDX2Cwn
👀 TV listings 👉 https://t.co/xliHcxWvEO pic.twitter.com/wafiZ8XmEz
Kane scored two goals on his World Cup debut as England left it exceptionally late to kick their 2018 World Cup campaign off with a narrow win over Group G rivals Tunisia.
The first was a simple tap-in to put the Three Lions ahead with 11 minutes played; the second was a 91st-minute winner to seal a dramatic 2-1 victory for Gareth Southgate's side in the dying seconds.
Kane scored five goals in his first two appearances at the 2018 World Cup after finding the net twice against Tunisia (see above) then following up with a hat trick in a 6-0 drubbing of Panama.
A further penalty against Colombia in the round of 16 saw the striker finish the tournament as Golden Boot winner, but the goal that technically secured the award was the strangest of the bunch.
Kane's third and final effort against Panama saw the England forward inadvertently find the net with a looping ricochet that deflected in off his heel from the edge of the area.
Kane once again led the scoring charts throughout England's Euro 2020 qualifying campaign by netting 12 goals in the space of just eight games, thus pipping Cristiano Ronaldo (11 goals for Portugal) to the top spot.
In a spree of formidable form, the striker scored in every one of the Three Lions' qualifiers and even found time to bag two hat tricks (against Bulgaria and Montenegro) but the vital 12th goal came in a 4-0 beating of Kosovo in the final outing.
Kane carried on his fine form into Euro 2020 itself, scoring four goals in seven games, as Southgate's ebullient side fought all the way to the final only to be ousted by Italy on penalties.
The captain failed to register at all during the group stage but soon put things right with a stooping header from a Jack Grealish cross in a 2-0 win over Germany in the round of 16.
England romped to a 4-0 win and went five points clear at the top of their World Cup qualification group with a clinical display in Budapest.
After Raheem Sterling had put the Three Lions ahead in the 55th minute, Kane added a second soon after, when he improvised in mid-air to nod home Sterling's heavily deflected cross.
England cantered to a 5-0 victory over Albania at Wembley on their continuing quest to seal qualification for the 2022 World Cup.
All five goals were scored before half-time with Kane finishing off both the rout and his own hat trick with an audacious scissor kick in a crowded penalty area.
Having moved level with the great Sir Bobby Charlton on 49 goals for his country with a penalty against Switzerland in a friendly at the tail end of March, Kane repeated the feat against Germany three games later to move clear of the 1966 World Cup-winning legend.
England had fallen behind in the Nations League clash in Munich but carved out a lifeline in the 88th minute when Kane was tripped in the area. He duly composed himself in order to dispatch the resultant spot kick and celebrated reaching a very rare milestone in international football.