Maurizio Sarri's men drew first blood at Anfield on Wednesday, knocking Jurgen Klopp's side out of the Carabao Cup thanks to Eden Hazard's glorious late strike.
But with both sides unbeaten in the Premier League so far, and both set to make significant changes to their line-up, this weekend's clash looks set to be even more intriguing.
Can the Reds make it seven from seven in the league? Can Chelsea underline their own impressive start to the campaign with a big home win?
Here, Goal takes a look at everything you need to know ahead of Saturday's meeting...
Liverpool will check on the fitness of defender Virgil van Dijk, who was forced off with a rib problem against Southampton last weekend and who missed the Carabao Cup game as a result. Klopp said the Dutchman was "in pain" earlier this week, but he is expected to shake off the problem to start.
Dejan Lovren made his first appearance of the season on Wednesday night, having been troubled by an abdominal problem since his return from the World Cup.
Adam Lallana will once more miss out, though he is closing in on a return from a hamstring issue. Divock Origi is expected to be out for another week with an ankle injury.
Alex Oxlade-Chamberlain and Rhian Brewster are long-term absentees.
Liverpool do not have any suspended players for this game.
Likely Liverpool starting line-up
One thing is for sure, Liverpool will make numerous changes for this one.
Alisson Becker, Trent Alexander-Arnold, Andy Robertson, Gini Wijnaldum, Mo Salah and Roberto Firmino will all return, while Joe Gomez will partner Van Dijk, should the Dutchman recover.
The biggest question concerns the midfield, where James Milner, Jordan Henderson and Naby Keita will compete for two places alongside Wijnaldum. The smart money is on Henderson and Milner, given the nature of the fixture and Klopp's preference for solidity away from home.
Chelsea team news
Sarri, too, will make changes. The likes of Hazard, Olivier Giroud, Marcos Alonso, N'Golo Kante and Jorginho will all come back in to the side, though Chelsea have doubts over the fitness of defender Antonio Rudiger, who has a knock, and wide man Pedro, who suffered a shoulder injury in the Europa League win over PAOK Salonika a week ago.
Andreas Christensen was forced off at Anfield, putting extra pressure on Sarri defensively, should Rudiger fail to recover.
TV channel & kick-off time
The fixture will be broadcast live on UK TV this weekend, screened on BT Sport 1, kick-off 5.30pm.
In the United States the game can be watched live on television on NBC Sports, kick off 12.30pm ET.
Best Opta match facts
Chelsea haven’t won consecutive home Premier League games against Liverpool since a run of three victories between October 2004 and September 2006 under Jose Mourinho.
Liverpool’s run of 14 league games without a clean sheet against Chelsea is their longest such run against a specific opponent in the top-flight since a streak of 17 against Blackburn (between 1947 and 1995).
Liverpool have only lost more Premier League games versus Manchester United (28) than against Chelsea (20).
Liverpool are looking to win their first seven games to a top-flight campaign for only the second time, also doing so in 1990-91. The only side to win their opening seven games to a Premier League campaign were Chelsea in 2005-06 (first nine).
No side has scored more first half goals than Liverpool in the Premier League this season (10, level with Man City), while the Reds are the only side yet to concede in the opening 45 minutes.
Liverpool have only won one of their last eight away Premier League games against fellow ‘big six’ opponents (D3 L4), though it was against Spurs this season.
Chelsea striker Olivier Giroud has scored five goals in his last six Premier League starts against Liverpool, including the winner in this exact fixture last season.
Chelsea’s Eden Hazard has scored four goals in his last two Premier League home games – as many as he had in his previous 17 at Stamford Bridge in the competition.
Liverpool boss Jurgen Klopp has won two of his three Premier League away games against Chelsea (67%) – the best win rate for visiting managers at Stamford Bridge in the competition (minimum 3 games).
Liverpool duo Mohamed Salah and Sadio Mane have created more chances for each other than any other pair in the Premier League so far this season (10).