The Mexican club beat Al Sadd - managed by Barcelona legend Xavi Hernandez - 3-2 on Saturday to set up the tie at Khalifa International Stadium.
It will be the first time Liverpool and Monterrey have met for a competitive fixture and so ahead of the inaugural clash, we tracked down ESPN FC's Mexican football correspondent Tom Marshall (@mexicoworldcup) to give us the lowdown on Antonio Mohamed's Liga MX side...
How did Monterrey qualify for this tournament?
Monterrey reached the Club World Cup by winning the CONCACAF Champions League for the fourth time this decade, last May.
Rayados (the team's nickname) defeated local city rivals Tigres 2-1 on aggregate in the final. It was an intense series, with the second leg played in front of 51,000 fans in Monterrey's Estadio BBVA.
What were the club's expectations going into the Club World Cup? Have they changed?
It's an interesting one because teams from CONCACAF tend not to do too well in the competition, in part because qualifying (the CONCACAF Champions League final) is usually in April or May and in the Mexican game form can change very quickly. But Monterrey have picked up some good results over the last three months and are looking to cause a shock.
Manager Antonio Mohamed has said his side are in Qatar to win, but if Monterrey can compete well with Liverpool and win the third-place play-off, the tournament will undoubtedly go down as a success.
Tell us about the manager...
Argentine Mohamed is pragmatic in his outlook.
The 49-year-old has only been in charge of Monterrey since October 9 but knows the club inside out having also managed them from 2015 until 2018.
Mohamed has won two Liga MX titles and the Copa Sudamericana with his first club Huracan. He re-joined Monterrey after an unsuccessful spell in Spain with Celta Vigo.
How does he like his team to play?
Mohamed's teams are more direct than the vast majority in Mexico and there's not as much emphasis on playing out from the back. Monterrey like to play on the counter.
Against Liverpool, Mohamed has already said his strategy will be to press high all over the pitch, try to force Liverpool into mistakes and basically have a go at the European champions.
It's a risky approach, but Mohamed's belief is that it'll be hard for Monterrey to create anything if the Mexican team only sit back.
Who is the star of the team?
Rodolfo Pizarro. The silver-haired 25-year-old is an increasingly important piece of the Mexican national team, is technically outstanding and will be looking to impress against Liverpool. Pizarro can play on either wing but will likely feature as a No.10 against Liverpool.
Keep an eye out too for 22-year-old central midfielder Carlos Rodriguez, who appears set for a long career at international level. Also, the former Tottenham striker Vincent Janssen is with the Monterrey squad in Qatar, but won't feature due to injury.
What is the team's biggest strength?
Rayados have plenty of strength in depth, with 18 full internationals in the squad, but in terms of an on-field strength it'd have to be Monterrey's counter-attacking. Dorlan Pabon and Jesus Gallardo down the wings have genuine pace and the team tries to get the ball to them quickly.
What is the team's form like heading into the competition?
Excellent. Monterrey may not have been great against Al Sadd, but are full of confidence after going on a 14-game undefeated streak since Mohamed took over. Monterrey advanced to the Liga MX 2019 Apertura final before jetting off to Qatar and will face Club America on December 26 and December 29 for the Mexican title on their return.
How do you expect Monterrey to line up against Liverpool?
Monterrey tend to play a 4-2-3-1 or 4-4-1-1, although Mohamed sometimes moves to a back three in-game. I expect the starting XI to be the same that started against Al Sadd in the quarter-final, except for Paraguayan Celso Ortiz coming in to replace Jonathan Gonzalez in central midfield.
What's your score prediction?
Monterrey 2-1 Liverpool.