A last minute goal by debutant Eric Dier ensured Mauricio Pochettino claimed his first win as Tottenham Hotspur manager, with Sam Allardyce's men missing glorious chances in an exciting match at Upton Park.
On Allardyce's 25th year of management and 400th Premier League match in charge, the signing from Sporting Lisbon spoilt the party as both teams went down to 10 men.
The last time these two teams met on the opening day of the season was in the 1999/2000 season when Frank Lampard scored the winner for a then Harry Redknapp side.
Despite the visitors having most of the possession in the first five minutes, West Ham had the first shot. Carlton Cole's hopeful 25 yard effort failed to trouble Hugo Lloris.
Midfield playmaker, Christian Eriksen forced Adrian into his first save of the season after eight minutes from a 25 yard free-kick, which the Spaniard dealt with comfortably.
Stewart Downing's delightful cross found Cole in the box, however, the former England international couldn't quite control the ball, and the Spurs' defence cleared there lines after 17 minutes.
Moments later the same situation happened for Cole, with the same result as he failed to find a gap through the Tottenham backline, and the score remained goalless.
Downing's crosses were looking dangerous, with the winger's latest delivery evading Cole, Collins and Vaz Te. The Hammers started to threaten Lloris at last.
Debutant Cheikhou Kouyate had the hosts' best chance when his glancing header from a whipped Downing ball beat Lloris, but went narrowly passed the left hand post.
However, after 28 minutes, moments of last year's home game came flooding back for Spurs.
Kevin Nolan's shot on the turn hit the hand of Kyle Naughton in the box, and the full back was given his marching order. What the Hammers fans didn't see coming was Mark Noble missing his spot, and the game remained 0-0.
West Ham piled the pressure on against the 10 men of Tottenham. Noble's corner found Ricardo Vaz Te lurking at the back post, but his drilled effort went wide.
Five minutes before half time, Aaron Lennon's curling effort had Adrian scrambling, but the ball landed on the roof of the net. At the other end Joey O'Brien's cross found a charging Vaz Te, whose header was caught by Lloris to cap off a very entertaining first half.
The second half began, and after 52 minutes Downing's long range strike was awkward for Lloris to handle as West Ham looked to capitalise on the one man advantage.
On the 63rd minute, both teams had the same number of players on the pitch, as James Collins was sent off for a second bookable offence after a foul on striker Emmanuel Adebayor. From the resulting free-kick, Eriksen sent the ball over.
Just short of the 70 minute mark, Andros Townsend's thunderbolt from 25 yards out forced Adrian into a magnificent stop, as the game became more open.
After some resilient play from Kouyate, Noble raced towards Lloris, but the French shot stopper pulled off a good block to deny him after 73 minutes. Moments later, Allardyce handed a home debut to Ecuador striker Enner Valencia in place of Cole.
The best chance of the interval fell to Downing. Nolan's neat flick found the winger, but Downing got the ball stuck under his feet, and Lloris dealt with the situation well. Adrian then dived well to his left to save from a Nabil Bentaleb strike from outside the box.
But in injury time, disaster hit West Ham as Harry Kane fed a beautiful through ball to full back and debutant Dier, who rounded Adrian and tucked home nicely and claim all three points against their local rivals.
West Ham: Adrian, O'Brien (Demel, 62), Reid Collins Cresswell; Noble, Kouyate, Downing, Nolan, Vaz Te (Diame, 68); Cole (Valencia, 80).
Subs: Jaaskelainen, Burke, Demel, Diame, Poyet, Zarate, Valencia
Tottenham: Lloris, Naughton, Kaboul, Dier, Rose; Capoue, Bentaleb, Lennon (Townsend, 61), Eriksen, Lamela (Holtby, 61), Adebayor (Kane, 81).
Subs: Friedel, Dawson, Davies, Holtby, Townsend, Soldado, Kane.
Attenndance: 34,977
Jack Pinnock