Arne Slot's side are only club in the competition with a perfect 12 points after four matchdays, leaving them 17 places better off than the indifferent holders in the 36-team standings.
Match preview
It is only fitting that Slot is set to embrace Carlo Ancelotti after joining the Italian in an exclusive managerial club on Sunday, where a Mohamed Salah-inspired Liverpool produced a gritty second-half turnaround to sink Southampton 3-2 in their top vs. bottom battle.
Before making yet more contract-related headlines with bombshell post-game comments, the indomitable Salah had the last laugh on the wet and windy South Coast with the game-winning brace, securing Slot's 10th win from his first 12 Premier League matches in charge.
Only Guus Hiddink and Ancelotti himself can boast as exceptional a record from their first 12 games in the competition, where Liverpool benefitted from another Manchester City capitulation to extend their insurmountable lead at the top of the table to eight points ahead of Sunday's blockbuster bout with the holders.
Also looking down on all of their Champions League counterparts, Liverpool's 4-0 pummelling of Bayer Leverkusen on matchday four means that they are the only side still boasting an unblemished record in the 2024-25 tournament; only in the 2021-22 campaign have they won their first five Champions League matches.
The Reds' display at St Mary's was lethargic and leggy at times, but Salah's everlasting excellence means that Liverpool have now scored at least two goals in each of their last six matches across all competitions, and the time is surely nigh to end their disheartening winless sequence against the holders.
Including the 2018 and 2022 finals, Liverpool are enduring an excruciating eight-game winless run against Real Madrid, who have won seven and drawn one of their last eight meetings with their Merseyside rivals since a 4-0 Anfield annihilation all the way back in 2009.
However, Ancelotti's troops have already failed two examinations of their title credentials in the new-look competition, October's surprise 1-0 loss at Lille and the humbling 3-1 home defeat to AC Milan on November 5, where former Blancos striker Alvaro Morata returned to haunt his erstwhile employers.
Lying smack-bang in the middle of the UCL rankings, Real's 18th-placed standing would not even suffice for a seeded path to the playoffs, but the 15-time European champions appear to have flipped a switch since being put to the sword by Milan.
Wednesday's visitors have won their last two La Liga matches by an aggregate scoreline of 7-0, hitting Osasuna for four without reply before the international break and easing to a 3-0 success over Leganes over the weekend, moving to within four points of a stuttering Barcelona at the top of the rankings.
Reeling in the Blaugrana is no longer Real's priority for the moment, though, as Los Blancos endeavour to avoid an unwanted fate that they are yet to experience in the Champions League - losing three group stage/league phase games in a single season.
The holders' recent memories of playing in front of the Kop are as fond as they could be, though, as they embarrassed Jurgen Klopp's Liverpool 5-2 in the 2022-23 UCL last 16, before completing the formalities with a 1-0 second-leg success in the Spanish capital.
Liverpool Champions League form:
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Liverpool form (all competitions):
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Real Madrid Champions League form:
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Real Madrid form (all competitions):
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Team News
Liverpool received just the one injury boost for their trip to Southampton, where Harvey Elliott made a matchday squad for the first time in over two months following a foot fracture, but all of Alisson Becker (hamstring), Diogo Jota (abdominal), Federico Chiesa (fitness) and Trent Alexander-Arnold (hamstring) missed out.
Slot has already conceded that rumoured Real target Alexander-Arnold is the only member of the quartet who might be in with a chance of coming back on Wednesday, where a couple of changes will no doubt be in store after a slightly worrying overall display at St Mary's.
Two members of the South American contingent - Alexis Mac Allister and Luis Diaz - ought to force their way back into the hosts' lineup in place of Curtis Jones and Cody Gakpo, as was the case with just over an hour played on Sunday.
From boosts to blows, Real Madrid will seemingly have to cope without Brazilian wing wizard Vinicius Junior for the trip to Anfield, as the club revealed on Monday morning that he had suffered a hamstring injury in the Leganes victory without giving a recovery timeframe.
Reports have suggested that Vinicius will be sidelined for a few weeks, though, and he joins long-term knee victims David Alaba, Dani Carvajal and Eder Militao in the medical bay, which also houses Rodrygo (muscle), Aurelien Tchouameni (ankle) and Lucas Vazquez (muscle).
Ancelotti did not rule Tchouameni or Vazquez out of the midweek game when questioned on Sunday, but the champions will most likely travel to Anfield with an identical squad from their triumph over Leganes.
Should Vinicius miss out as expected, Brahim Diaz will be expected to fill the void in the final third, and Real's crisis at the back means that a Champions League debut awaits 21-year-old Castilla graduate Raul Asencio.
Liverpool possible starting lineup:
Kelleher; Alexander-Arnold, Konate, Van Dijk, Tsimikas; Gravenberch, Mac Allister; Salah, Szoboszlai, Diaz; Nunez
Real Madrid possible starting lineup:
Courtois; Valverde, Asencio, Rudiger, Mendy; Camavinga, Modric; Guler, Bellingham, Diaz; Mbappe
We say: Liverpool 3-1 Real Madrid
All football aficionados know to never count Ancelotti's Real Madrid out in the Champions League, and Liverpool were far from their scintillating best against Southampton, but the magnitude of Wednesday's occasion should mean that there is no similar complacency from Slot's team.