Three first-half goals from Missy Bo Kearns, Rhiannon Roberts, and Rachel Furness, accompanied by a second-half strike from Katie Stengel would leave Lydia Bedford's Leicester in third position of Group B.
There were nine changes to the side who lost to Manchester Utd in the WSL at the weekend, with Ellen Jones making her first full debut for the Foxes.
Amongst the other changes were, Demi Lambourne and Abbie McManus, who come into the starting XI for the first time this season, having recovered from injury, with the former taking responsibility of the armband for tonight's cup clash.
The opening 10 minutes of the game saw both sides battle hard for possession, but it was the visitors who were most dangerous, with a succession of corners proving a threat to Leicester's goalmouth.
In the 14th minute, Liverpool's pressure paid off, as Missy Bo Kearns fired a low right-footed shot, past Lambourne, from the edge of the City box.
The opener sparked the Foxes into life, who, under Bedford's instructions, started pushing the Liverpool backline, and taking a more commanding position, higher up the pitch.
With 18 minutes on the clock, Leicester had their first chance of the game through Natasha Flint. Heavy pressure from the striker allowed the forward to win possession off of Liverpool's defence, on the edge of the Reds box. But, with probably more time than she realised, the No.7 saw her left-footed effort head over the bar.
Flint was heavily involved again, four minutes later, when she laid off a chance for Mackenzie Smith, however, City's Academy player snatched at the ball, and the chance was gone.
Despite a period of sustained pressure from Leicester, it was Liverpool who scored the second goal of the game, as goalscorer, Bo Kearns, changed to provider, with a dangerously delivered corner which was headed home by Roberts.
Just after the half-hour mark, LCFC Women had their best chance of the half. Picking up the ball from 35 yards out, Monique Robinson tried her luck from range, and sent a powerful, dipping effort towards Eartha Cumings' goal. But, as the shot had the keeper beat, the rattling crossbar would leave Robinson with a head-in-hands moment.
Seconds before the interval, the visitors took a commanding lead as Liverpool skipper, Furness, would earn a standing ovation from the travelling supporters, thanks to a left-footed, curling effort from the edge of the box which flew past the helpless Lambourne into the top corner of the net.
The start of the second-half saw City looking for a way back into the game. It was winger, Ava Baker, who had the first chance, when CJ Bott picked out the youngster on the edge of the box with a cross, but the following shot was high and wide.
Bott continued to provide an outlet for the Foxes, with a number of dangerous crosses, including one from the left-hand side, which found Carrie Jones on her own, a few yards out. Instead of going for goal, the substitute attempted to nod the ball into the path of Flint, but the striker was inches away as she saw the ball flash past her and out for a goal-kick.
A handful of changes saw more experienced players, such as Aileen Whelan, introduced during the second-half. However, in a period of control from Leicester, it was Liverpool who found the net once more, when Katie Stengel drove into the Leicester half, before firing an effort past Lambourne in the 72nd minute.
There would be a few more dangerous crosses for Leicester, which sadly, could not come to fruition, before the referee's whistle blew, bringing an end to proceedings.
The full-back in action at Pirelli Stadium.
The highlight of the game was supplied by Liverpool's captain, Rachel Furness, who found the net with an impressive curling effort, moments before the break. The edge of the box strike confirmed all three points for the team from Merseyside.
The Academy midfielder striking at goal during the first half.
With a number of Academy players and graduates involved in the starting squad, it was a strong test for the young Foxes, who produced determined performances, and Monique Robinson will be disappointed to not come away with a goal, following her impressive strike in the first-half.
Where do we stand?
The defender against Liverpool.
The defeat leaves Leicester third in League Cup Group B, with three points from the opening two games. Meanwhile, the Foxes remain 12th in the WSL, and still searching for a first league win.
Baker battling for possession with Liverpool's Rhiannon Roberts.
It's a quick turnaround for LCFC Women as they return to WSL action this weekend, with an all-important away fixture against Reading FC on Sunday (2pm GMT kick-off), at the Select Car Leasing Stadium.
City: Lambourne (C); Bott (Simon 65'), McManus, Tierney (Howard 46'), Vance; Robinson (Green 46') (Whelan 65'), Scofield, Smith; E. Jones (C. Jones 46'), Flint, Baker.
Subs not used: Poor, Goodwin, Purfield, Pike.
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