The hosts have been in superb form domestically so far this term, building a six-point lead at the top of the Premier League table, whereas Arsenal are already 12 points behind them and go into this game off the back of a damaging 2-2 draw with Crystal Palace on Sunday.
It may only be 10 matches into the Premier League season, but already Liverpool have showcased some classic hallmarks of champions, and the latest of those arrived on Sunday.
Anfield was stunned into silence when Tottenham Hotspur took the lead through Harry Kane after just 47 seconds, presenting a serious test of Liverpool's character having dropped their first points of the campaign in an under-par display against Manchester United a week previously.
However, the Reds hit back to dominate the following 89 minutes and goals from Jordan Henderson and Mohamed Salah ultimately saw Jurgen Klopp's side restore their six-point lead at the top of the table having recorded the joint-best start to a campaign in Premier League history.
Not including the Community Shield it is now 28 matches and almost 10 months since Liverpool last tasted defeat in a domestic contest of any kind, although their only silverware under Klopp has come in Europe and that is something they will desperate to fix this season.
The Premier League remains the holy grail, of course, and it is safe to say that the EFL Cup is at the bottom of their priority list, but winning is a habit that Liverpool will be desperate to continue regardless of the competition.
The Merseysiders had suffered back-to-back third-round exits and lost four EFL Cup games in a row before their triumph at MK Dons last month, and even then there was speculation that they could still be eliminated at the first hurdle after fielding an ineligible player.
Such a severe punishment was avoided as Liverpool were rewarded with this glamour last-16 tie, and they will now aim to make the most of their reprieve by going all the way and lifting their first piece of domestic silverware since 2012.
Liverpool are the most successful club in this competition's history with eight previous wins, whereas Arsenal have only won it on two previous occasions and not since 1992-93.
Considering the success the Gunners have enjoyed since then, an assumption can be made that they do not take the EFL Cup as seriously as the other competitions they are in, but a win over Liverpool at Anfield on Wednesday would provide a much-needed morale boost for Unai Emery's side.
Questions over Arsenal's mental resolve have resurfaced again following defeat at Sheffield United earlier this month and Sunday's 2-2 draw with Palace, which saw them throw away a two-goal lead at home to their London rivals.
While VAR played its part in that contest, the main talking point surrounded Granit Xhaka's reaction to being booed off the field by his own fans, with the club captain cupping his ears and seemingly swearing at the supporters before angrily taking his shirt off and heading straight down the tunnel.
Not even Emery could defend Xhaka's actions, and calls for him to be stripped of the armband could yet come to fruition, with the hierarchy expected to hold talks over the situation this week.
The furore surrounding Xhaka's actions risk masking the fact that Arsenal dropped more points which they should have had wrapped up, though, and their only win since the last international break was a somewhat fortuitous one over Vitoria Guimaraes in the Europa League, when only two sublime free kicks from Nicolas Pepe in the final 10 rescued them.
Manchester United and Tottenham's struggles mean that Arsenal still sit fifth despite their inconsistent form, but they are 12 points off Liverpool's pace after only 10 games, while the gap to fourth place has now grown to four points.
The main positive to come out of Arsenal's season so far has been the emergence of some of their youngsters, and that was particularly prevalent in the last round of this competition as they thrashed Nottingham Forest 5-0.
Liverpool will, of course, pose a much bigger problem as the Gunners aim to reach the quarter-finals for a fourth successive year but, given the tournament, Emery can at least expect a different proposition to the one which faced his side when they were beaten 3-1 at Anfield in August.
Liverpool EFL Cup form: W
Liverpool form (all competitions): WWWDWW
Arsenal EFL Cup form: W
Arsenal form (all competitions): DWWLWD
Salah was forced off with five minutes remaining of Sunday's match after seemingly picking up another ankle injury, although he was back in training on Monday morning and the problem is not thought to be serious.
Nevertheless, the Egyptian, who scored twice in the Premier League meeting between the two sides in August, may not be risked in a Liverpool XI which is likely to show a number of changes.
Fringe players such as Naby Keita, Adam Lallana and Divock Origi will be hopeful of a run-out, while youngsters Ki-Jana Hoever, Harvey Elliott, Rhian Brewster and Curtis Jones were among the players to start in the previous round.
Whether Klopp opts for such inexperience against higher-calibre opposition remains to be seen, although Arsenal are also expected to give youth a chance.
Mesut Ozil is another who will be hopeful of a start, having featured in the last round but not played a minute of football since for the Gunners.
Liverpool possible starting lineup:
Adrian; Milner, Lovren, Gomez, Robertson; Oxlade-Chamberlain, Henderson, Keita; Lallana, Brewster, Origi
Arsenal possible starting lineup:
Martinez; Bellerin, Holding, Mustafi, Kolasinac; Torreira, Willock; Maitland-Niles, Ozil, Saka; Martinelli
We say: Liverpool 2-0 Arsenal
The fortunes of these two sides in the Premier League are of less relevance in this match considering the number of changes expected to both teams, but Liverpool appear to have the greater strength in depth. The Reds seem almost invincible at Anfield at the moment, and we suspect that winning habit will continue on Wednesday.