Tottenham's woes at Wembley continued with a 2-1 defeat to Chelsea in their first league game at their temporary home.
After exquisitely putting the champions ahead with a first-half free-kick, Marcos Alonso snatched a dramatic win in the 88th minute with a shot that Spurs captain Hugo Lloris will feel he should have saved, six minutes after Michy Batshuayi's own goal had levelled the contest.
It means Spurs have now lost their last four games against their London rivals at Wembley, and have only tasted victory at the national stadium once since beating the Blues in the 2008 League Cup final.
Chelsea, meanwhile, bounce back from their opening-day defeat by Burnley with the first win of their title defence.
Tottenham: Lloris (5), Trippier (5), Alderweireld (6), Vertonghen (6), Davies (5), Wanyama (5), Dembele (6), Dier (5), Eriksen (7), Alli (5), Kane (6).
Subs: Son (6), Janssen (n/a), Sissoko (4).
Chelsea: Courtois (7), Christensen, (5) Rudiger (5), Luiz (6), Azpilicueta (5), Alonso (9), Moses (5), Kante (6), Bakayoko (6), Willian (5), Morata (6).
Subs: Pedro (n/a), Batshuayi (4).
Man of the match: Marcos Alonso
Having missed the crucial penalty in Chelsea's Community Shield defeat by Arsenal, Alvaro Morata was presented with the chance to atone five minutes into his first start for the champions, but he headed Cesar Azpilicueta's cross wide.
The miss failed to unsettle Chelsea as Spurs, having awoken from their early malaise, dominated possession but failed to test Thibaut Courtois, Dele Alli flashing a shot over on the 15-minute mark after Andreas Christiensen's error.
Just as Spurs looked to have taken control of the game they were undone by the brilliance of Alonso, who whipped an unstoppable free-kick over the lofty wall and the reach of Lloris.
The hosts rallied as Kane drew Courtois into action at his near post before fizzing a low drive through Antonio Rudiger's legs but a yard wide, before Christian Eriksen's wicked free-kick managed to evade everyone in the penalty area.
There was still time for more from Spurs as Kane rattled the post on 42 minutes and Ben Davies stung the palms of Courtois, but there was no way through.
Kieran Trippier and Victor Wanyama returned in place of Kyle Walker-Peters and Moussa Sissoko for Spurs, while Antonio Conte made four changes. With Gary Cahill and Cesc Fabregas suspended, Tiemoue Bakayoko, Alvaro Morata and Andreas Christensen started, while Victor Moses returned in place of Michy Batshuayi.
Barely a minute into the second half, Spurs had two glorious chances to equalise as Kane's back heel released Eriksen, whose shot was turned behind for a corner, from which Kane failed to connect with a free header from eight yards.
Spurs had appeals for a penalty denied on the hour by referee Anthony Taylor, who deemed Alli's cross to have struck Azpilicueta's chest. Chelsea had the chance to put the game to bed but Morata and Moses failed to convert chances, before Willian struck the post on 73 minutes.
And that opened the door for Spurs to equalise as Batshuayi turned Eriksen's free-kicked beyond Courtois, but Alonso had the last word, sending the travelling Chelsea contingent, and boss Antonio Conte, into raptures.
- Spurs' 19-game home Premier League unbeaten run has come to an end, with Chelsea the first side to beat Spurs away from home since Southampton in May 2016.
- Tottenham have lost seven of their last nine matches at Wembley (W1 D1) and lost each of their last four games against Chelsea there.
- Harry Kane had eight shots, his most in a Premier League game without finding the net.
- Kane has now had 34 shots and played 12 games in the month of August without scoring in the Premier League.
- Marcos Alonso has scored two direct free-kicks in the Premier League since the start of last season, with only Philippe Coutinho (3) scoring more.
Man of the Match - Marcos Alonso
A match-winning brace from the wing-back who continues to prove time and again that he knows where the goal is. His free-kick to open the scoring was sublime and he was in the right place to power home the winner, even if Lloris should have done much better with his effort.
Tottenham go in search of their first home win at Wembley when Burnley travel to the national stadium on Saturday. Chelsea, meanwhile, will look to do the same when they host Everton at Stamford Bridge on Sunday lunchtime.