Bassong only arrived from Newcastle for £8million last week, but he wasted no time winning over the home supporters as he rose above the vistors' defence to secure all three points for the home side.
Tottenham took the lead on the stroke of half-time when Benoit Assou-Ekotto fired a spectacular strike past Pepe Reina, but Steven Gerrard brought the Reds level from the penalty spot.
Rafa Benitez must have thought his side would go onto win the game, but he suffered a miserable start to the season when Bassong netted the winner and gave the Spaniard plenty to think about on his long journey back to Merseyside.
Tottenham had a golden chance to break the deadlock on 29 minutes when Luka Modric picked out Robbie Keane who was completely unmarked inside the box, but he directed his header straight at Reina who made a comfortable save.
Modric was involved in the heart of the action once again on 33 minutes when his superb pass picked out Keane who was clean through, but the Spurs skipper once again saw his effort well saved by Reina.
Keane wasted his third chance of the game on 41 minutes after Tom Huddlestone used great vision to pick out the Republic of Ireland striker, who was free inside the box but fired his shot high over the bar.
The home side finally got their just rewards when they broke the deadlock in spectacular fashion on 44 minutes.
Huddlestone saw his free-kick blocked by the Liverpool wall. The rebound fell to Assou-Ekotto whose powerful shot sailed past Reina into the top left-hand corner.
It was an extra special moment for the French defender who was celebrating the first goal of his career.
Reina had to be at his best once again for Liverpool on 52 minutes when he made a superb one-handed save to deny Wilson Palacios, whose shot looked destined for the top corner.
Tottenham were made to pay for all those missed opportunities when Gerrard grabbed an equaliser for Liverpool on 55 minutes.
Glen Johnson showed why Benitez paid £17million for his signature during the summer when he made a superb run into the Tottenham half.
The England defender cut inside Huddlestone and was then brought down inside the box by Heurelho Gomes. Gerrard made no mistake smashing the spot-kick into the roof of the net.
But Spurs quickly restored their lead on 59 minutes when Modric's free-kick picked out Bassong, who rose above Jamie Carragher inside the box and saw his powerful header fly past Reina into the corner of the net for the crucial winner.
Liverpool had strong claims for a penalty turned down on 87 minutes when the ball appeared to strike Assou-Ekotto's arm, but referee Phil Dowd waved for play to continue and their day was compounded when assistant boss Sammy Lee was sent off for dissent.