The 4-2 win continued Tottenham's impressive run of results under new trainer Harry Rednapp. Pavlyuchenko, who struggled to find form under previous trainer Juande Ramos following his summer move from Spartak Moscow, has now scored four goals in as many games.
Tottenham were facing Liverpool at their home stadium of White Hart Lane for the second time in less than two weeks, after beating the Merseysiders 2-1 in a Premier League match on November 1.
Pavlyuchenko was Liverpool's nemesis in that game, hitting home the winner in the last minute, and he was again the bane of the most successful side in English soccer's defense on Wednesday, striking from close range in the 38th minute after a pass by England Under-21 international Fraizer Campbell.
Both sides had made sweeping changes from their last Premier League games, and Campbell took advantage of more confusion in Liverpool's defense to slot home his first goal for the club in the 42nd minute. Three minutes later, the on-loan striker met an Aaron Lennon cross to head home goal number three.
Damien Plessis got one back for the guests straight after the break, heading home from a corner, but Pavlyuchenko tapped home from close distance in the 52nd minute to restore Tottenham's three-goal advantage. Another corner saw Sami Hyypia head in Liverpool's second in the 63rd minute, but Tottenham never looked in danger of surrendering their lead, and Pavlyuchenko could well have had a hat-trick, his fierce shot saved by Diego Cavalieri.
"We have three strikers who are firing on all cylinders," Rednapp said after the match.
In another Carling Cup tie on Wednesday, Chelsea, owned by Russian billionaire Roman Abramovich, were knocked out by humble Burnley, from the second tier of English soccer. The match finished 1-1, the guests winning on penalties. The penalty shoot out was the fifth in a row that Chelsea have lost, the most famous being the spot-kick decider in the 2007/08 Champions League final in Moscow in May.
