Steven Gerrard quickly equalized Jake Livermore's deflected opener in the first half, but disastrous defending let in David Meyler before Tom Huddlestone's shot was diverted in.
The Tigers first goal put the home side in front after 20 minutes at the KC Stadium on Sunday but a superb Steven Gerrard free kick, almost 15 years to the day since his Liverpool debut, brought things level.
But Hull was rewarded for a stirring second-half performance when Meyler reacted quickest to pick up a loose ball and fire in with 19 minutes remaining before Martin Skrtel's own goal settled the result.
The result catapults the hosts into the top half of the table and leaves Liverpool seven points adrift of Premier League leaders Arsenal.
Hull manager Steve Bruce made two changes from its defeat to Crystal Palace and Liverpool counterpart Brendan Rodgers made three alterations following the 3-3 Merseyside derby draw. Philippe Coutinho opened the scoring against Everton last Saturday but was one of those who dropped to the bench, while the injured Paul McShane was replaced by Alex Bruce for Hull.
The Tigers had lost four of its previous five Premier League games and, despite Liverpool's dominance of possession, it was the home side which created the first chance. A corner was cleared as far as Alex Bruce after 14 minutes and his teasing cross was glanced just wide by Curtis Davies.
Hull went in front six minutes later when Livermore and Meyler combined for the former to unleash a shot that took a wicked deflection off Skrtel and flew past Simon Mignolet, his first goal for the club since joining on loan from Tottenham.
But the lead was short-lived as Liverpool captain Gerrard produced a sumptuous free kick that he whipped into Allan McGregor's far corner from 25 yards.
Luis Suarez cut a frustrated figure for most of the half and missed a very presentable opportunity in the final minute of the opening period when Raheem Sterling found the Uruguayan on the left but his side-footed effort was tame and straight at McGregor.
Liverpool should have gone in front after 70 minutes when Coutinho's cross found Victor Moses, who met it on the volley but was denied at point-blank range by McGregor.
McGregor's save proved crucial as Hull regained the lead a minute later after the Reds failed to clear and Meyler picked up the loose ball and showed great composure before firing in his first goal of the season.
Suarez whistled a late free kick wide before Hull put the game out of reach with four minutes remaining when Huddlestone's effort was headed into his own net by the unfortunate Skrtel.