Two of Liverpool's most recent successes have come in penalty shootouts, winning by that method to claim the EFL Cup trophy back in 2022.
That was the ninth particular clash between Chelsea and Liverpool in this competition - the 10th scheduled for Wembley Stadium on Sunday - with all but two of those occasions coming within the last 19 years.
The first-ever League Cup tie took place in 1977, Kenny Dalglish and Jimmy Case getting on the scoresheet in a 2-0 victory at Anfield.
As many as 23 years passed by before another encounter in this tournament, Robbie Fowler scoring the extra-time winner as Liverpool emerged victorious by a 2-1 scoreline in a third-round fixture in November 2000.
Chelsea's first-ever win over Liverpool, and arguably their most significant, in this competition came in 2005 as they won 3-2 at the Millennium Stadium in Cardiff, Steven Gerrard scoring an own goal and Mateja Kezman famously scoring the winner in extra time.
That triumph represented Jose Mourinho's first trophy in English football, but the Portuguese had departed earlier in 2007-08 when Chelsea won 2-0 in a fifth-round tie at Stamford Bridge, Frank Lampard and Andriy Shevchenko getting on the scoresheet.
Almost four years would go by before Liverpool got their revenge at the same stage in 2011-12, Maxi Rodriguez and Martin Kelly netting in the second half as the Merseyside giants won a game that featured two much-changed starting lineups.
In the 2014-15 campaign, Chelsea and Liverpool would meet in the semi-finals, a young Raheem Sterling scoring a penalty for Liverpool after Eden Hazard's opener in the first leg at Anfield.
The tie would be decided in the second leg courtesy of Branislav Ivanovic's 94th-minute goal in extra time, Chelsea then going on to defeat Tottenham Hotspur in the final.
Next would come the dramatic third-round encounter in September 2018, Chelsea overturning Daniel Sturridge's opener through goals from Emerson Palmieri and Hazard, the latter scoring one of his most memorable strikes in a Chelsea shirt with seven minutes remaining at Anfield.
In what was the first of two Wembley finals in 2021-22, Liverpool would win the EFL Cup in February 2022, an entertaining goalless draw being followed by a penalty shootout that featured 21 successive conversions before Chelsea goalkeeper Kepa Arrizabalaga sent his spot kick high over the crossbar, gifting Liverpool an 11-10 triumph and their ninth League Cup trophy.
LEAGUE CUP HEAD-TO-HEAD RECORD
August 30, 1977: Liverpool 2-0 Chelsea (second round)
November 1, 2000: Liverpool 2-1 Chelsea (third round)
February 27, 2005: Chelsea 3-2 Liverpool (final)
December 19, 2007: Chelsea 2-0 Liverpool (fifth round)
November 29, 2011: Chelsea 0-2 Liverpool (fifth round)
January 20, 2015: Liverpool 1-1 Chelsea (semi-final, first leg)
January 27, 2015: Chelsea 1-0 Liverpool (semi-final, second leg)
September 26, 2018: Liverpool 1-2 Chelsea (third round)
February 27, 2022: Chelsea 0-0 Liverpool (Liverpool win on penalties, final)