While that match evokes past and present glory, Barcelona play Ajax Amsterdam in another Champions League match between European aristocracy with eight European Cup wins between them.
The game between AS Roma and Bayern Munich in Rome, another heavyweight affair, gives Francesco Totti another chance to beat his own record as the oldest man to score in the competition.
Real, the reigning European champions, have lost all three competitive European matches they have played against Liverpool: the 1981 European Cup final when Liverpool beat them 1-0 in Paris as well as 4-0 and 1-0 defeats in the last 16 of the Champions League in 2009.
But Real arrive for their Group B match in great form, having won their last seven matches in all competitions following their second successive 5-0 win in La Liga, over Levante on Saturday.
Liverpool meanwhile will need to improve on their somewhat fortunate 3-2 Premier League win over Queens Park Rangers on Sunday when they needed the help of two own goals from the struggling London side for a late victory.
Still, coach Brendan Rodgers says he is keen to face Real on Wednesday.
"Real Madrid are playing as well as they have played for the last five to 10 years, the threats they have," he said after the QPR game. "I am really looking forward to that."
Real's win at Levante featured another two goals from Cristiano Ronaldo, who has now scored 15 goals in seven La Liga starts this season.
Real coach Carlos Ancelotti, always keen to do well against Liverpool after they beat his AC Milan side on penalties in the famous 2005 final in Istanbul after trailing 3-0 at halftime, has two big games ahead of him this week.
After the trip to Anfield comes the first Clasico of the season against Barcelona next weekend.
"We are on a good run but we need to remember that behind the goals there is sacrifice, fight and concentration. You don't score without sacrifice and concentration. The best players realise that," Ancelotti said.
DON'T LOOK BACK
Barcelona's Javier Mascherano believes that Tuesday's visit of Ajax will not only help get their Group F campaign back on track, after losing 3-2 to Paris St Germain three weeks ago, but also prepare them for the Clasico.
Barca beat a resolute Eibar 3-0 on Saturday with Lionel Messi taking his Liga tally to 250 goals and Mascherano says it is important Barca keep winning and do not look back to the past after they beat Ajax 4-0 at the Nou Camp in last season's group stage.
"You cannot live in the past for games that are going to take place in the future. The match against Ajax is important for us and we need to be fully focused on that," said the Argentina midfielder.
"If we don't play well on Tuesday then that can also change the mood and we want to play well and be ready for the Clasico," he said.
The atmosphere at Anfield and the Nou Camp will be fantastic, which is more than can be said for the one the players of CSKA Moscow and Manchester City will experience in Moscow, with their Group E match being played behind closed doors on UEFA's orders because of the continuing troublesome behaviour of CSKA's fans.
When the two clubs met in the group stage last year, CSKA's fans racially abused City's Yaya Toure and had one of their stands closed, but following continued trouble this will be their second successive European game without fans after their opening 1-0 defeat by Bayern Munich last month.
City who beat CSKA 2-1 in Moscow last season, could well kick start their stuttering campaign with another win there after losing their opener 1-0 to Bayern Munich and drawing 1-1 at home to AS Roma three weeks ago.
Tuesday's Roma-Bayern match should also be one of the week's highlights. While Bayern's defence appears impregnable, Roma have scored in each of their nine games this season.
Totti became the oldest scorer in the Champions League era at 38 years and three days when he netted for Roma against City three weeks ago and has been a fundamental part of Roma's resurgence under French coach Rudi Garcia.
Totti also scored the winner when Roma beat Bayern 3-2 almost exactly four years ago.
But Bayern, unbeaten in 11 games in all competitions, have kept eight successive clean sheets and have not conceded a goal since the 1-1 draw against Schalke 04 on August 30, a total of 748 minutes.