Having weathered early pressure from the visitors, the Reds steadily asserted themselves and created a series of chances either side of half-time.
The breakthrough eventually came against his former club from Daniel Sturridge – who made amends for an earlier miss by emphatically volleying beyond Willy Caballero on 59 minutes.
But the Blues overturned their deficit in the final stages, Emerson equalising before substitute Eden Hazard slammed in a winner for Maurizio Sarri’s men and eliminated Liverpool.
Team news
Jürgen Klopp made eight changes to his starting XI for the first of back-to-back meetings with Chelsea, including a full debut for summer signing Fabinho.
The first half
The brisk nature of the passing in the early stages offered conclusive evidence of both sides’ intentions in the competition.
It was Chelsea who enjoyed the better of the initial jousting, however. Andreas Christensen was first to a corner in from the right flank but sent his header straight at Simon Mignolet, before the Liverpool goalkeeper smartly collected a low drive from Willian.
Mignolet, making his first appearance of the season, was then called on for two crucial saves to deny Alvaro Morata in quick succession.
Cesc Fabregas’ precise lofted pass into the Reds box eluded Dejan Lovren and found the Chelsea striker in behind – but his dinked effort was blocked at close range.
Moments later, Morata snuck into space near the left edge of the area to collect Willian’s pass, turned inside Joel Matip and snapped a strike towards the near post that Mignolet palmed away.
Liverpool did begin to settle and the home fans launched an unsuccessful appeal for a penalty on the half-hour mark when Naby Keita went down as he looked to move Sturridge’s square pass around Gary Cahill.
The Reds No.8 tried to take matters into his own hands soon after, shuffling inside Cesar Azpilicueta and walloping a shot towards the top right corner that Caballero clawed away on the stretch.
Chelsea’s stopper was their saviour again within two minutes. Xherdan Shaqiri raced clear on the right and cut back inside to clip a diagonal to Sadio Mane – but the Senegalese’s header back across goal was just about halted.
The second half
Liverpool should have broken the deadlock 30 seconds after the restart.
Christensen’s poor back pass was a gift for Sturridge, who rounded Caballero to his right but unexpectedly prodded wide of the open goal.
Fortune clearly wasn’t in the home side’s favour. Mane was somehow denied next; when Matip sent a clearance back into Chelsea territory, Ross Barkley’s header drifted into his own box – but the final strike flicked against the Blues ‘keeper and off target.
Their luck changed just before the hour, though.
Mane’s knock into Keita from the left flank allowed the latter to shimmy away from Azpilicueta and blast at goal – Caballero made the save yet again but only punched the ball out to Sturridge, who acrobatically slammed it into the net.
The Reds were on top on the scoresheet and in terms of control but their slender lead was eradicated 11 minutes before full-time.
Barkley was the first man to a free-kick whipped from the right wing to the near post and though Mignolet repelled the midfielder’s effort, Emerson was primed to convert the rebound.
Sturridge went agonisingly close to restoring Liverpool’s advantage when a slick move involving Shaqiri and Roberto Firmino teed up the No.15 to send a sweeping curler off the crossbar.
Instead, it was Chelsea who produced the decisive goal. Hazard was the creator and scorer in one, dribbling through Alberto Moreno and Keita and smacking a shot across Mignolet into the far corner to knock the Reds out.
The stats