Lee Carsley's second-half winner settled the 200th Merseyside derby.
Carsley scored from 20 yards past a motionless Liverpool goalkeeper Chris Kirkland after he was set up by the impressive Leon Osman after 68 minutes.
In a tense encounter, both sides had glorious opportunities before Carsley struck to move Everton up to second place in the Premiership.
Tim Cahill missed a headed chance, while Everton's Nigel Martyn saved well from Neil Mellor and Steven Gerrard.
It was Everton's first win over Liverpool for five years and put them 12 points clear of their arch-rivals.
Liverpool dropped Steve Finnan and Xabi Alonso to the bench, bringing in Josemi and Dietmar Hamann.
The opening exchanges were predictably fierce, but Everton created and wasted the first clear opportunity after 21 minutes.
Thomas Gravesen released Bent, and his perfect cross was met by Cahill, who somehow headed wide from only six yards.
Salif Diao was acting as Liverpool's midfield enforcer, and it was no surprise when he was booked for the latest in a succession of fouls, this time on Cahill.
Liverpool had an opportunity that was just as inviting as Cahill's after 32 minutes, but they also wasted the chance.
Gerrard's free-kick found Mellor inside the six-yard box, but his point-blank header was brilliantly blocked by Martyn and Alan Stubbs scrambled clear.
Osman was dangerous on Everton's right-flank, and it took a desperate interception from John Arne Riise to stop him forcing an opening for Bent as the interval approached.
Diao had an early opportunity after the break, half-volleying narrowly over after Everton failed to clear another Gerrard free-kick.
Liverpool started the second-half in control, but Riise was booked by referee Steve Bennett for a foul on the busy Cahill.
Josemi had suffered an uncomfortable afternoon, and he picked up an inevitable caution for a foul on Kevin Kilbane.
Everton broke the deadlock after 68 minutes through Carsley.
Osman set up the Republic of Ireland midfield man, and his shot from 20 yards beat Kirkland, with questions sure to be asked about the goalkeeper's positioning.
And seconds later Riise had to kick off the line from Cahill as Everton went for the kill.
Gerrard, who scored the wonder goal that beat Olympiakos in the Champions League, missed a glorious chance to put Liverpool level with 15 minutes left.
The ball fell perfectly for the Liverpool captain on the edge of the area, and he fired inches wide with Martyn well beaten.
Both sides made substitutions immediately, with Duncan Ferguson replacing the tireless Bent and Djimi Traore coming on for Florent Sinama Pongolle.
Gerrard was driving Liverpool forward, and it needed a fine save from Martyn to deny him again after 78 minutes.
Liverpool mounted a belated rally, and Cahill needed to scramble off the line in the dying seconds as Traore pressurised Martyn.
Everton: Martyn, Hibbert, Stubbs, Weir, Pistone, Carsley,
Osman (Watson 87), Gravesen (Yobo 83), Cahill, Kilbane,
Bent (Ferguson 76).
Subs Not Used: Wright, McFadden.
Booked: Hibbert, Ferguson.
Goals: Carsley 68.
Liverpool: Kirkland, Josemi, Carragher, Hyypia, Riise,
Diao (Alonso 78), Hamann (Nunez 66), Gerrard, Kewell,
Sinama Pongolle (Traore 75), Mellor.
Subs Not Used: Finnan, Dudek.
Booked: Diao, Riise, Josemi.
Ref: S Bennett (Kent).