While the hosts are looking forward to their 11th World Cup appearance, Chile will begin a new era under Eduardo Berizzo after failing to qualify for Qatar.
Match preview
South Korea eased through the second stage of qualifying before finishing in second place in the third round to book their place at a tenth consecutive World Cup.
In their 16 qualifying games across the two rounds, South Korea lost just once, while they emerged victorious on 12 occasions.
Following their qualification, Monday's hosts were drawn in a World Cup group alongside Portugal, Uruguay and Ghana, with preparations for those contests already underway in the current international window.
Paulo Bento's side took part in the first of four friendlies on Thursday, suffering a heavy 5-1 defeat to Brazil, but they now turn their attention to Monday's home meeting with Chile.
Despite losing in their last outing, Hwang Ui-jo's strike against Brazil ensured South Korea have now scored in 11 of their previous 12 games, and they will be aiming to continue that impressive run on Monday.
Chile's dreams of a 10th World Cup appearance will have to wait until at least 2026 after they failed to qualify for the 2022 finals.
La Roja finished five points adrift of the playoff place, losing nine of their 18 qualifying matches - only Bolivia and Venezuela lost more games in the COMNEBOL section of qualifying.
The failure to reach Qatar resulted in the departure of Martin Lasarte, who left after spending just over a year at the helm of the Chilean national team.
Berizzo has been named as Lasarte's successor and the new boss will take charge of his first game as Chile's head coach on Monday.
The new manager will be hoping to start with a positive result, and recent friendly results suggest that may be possible, with the visitors unbeaten in their last five international friendlies.
South Korea International Friendlies form:
South Korea form (all competitions):
Chile International Friendlies form:
Chile form (all competitions):
Team News
With three friendlies still to play in the current international window, South Korea could give game time to the majority of the squad over the course of those three matches.
Goalkeeper Jo Hyeon-woo could be given an opportunity to impress against Chile, while Kim Moon-hwan is expected to start at right-back.
Monday's contest could also be a momentous occasion for Tottenham Hotspur's Son Heung-min, who is in line to make his 100th appearance for his country.
As for Chile, they have decided to name a relatively inexperienced squad, giving the likes of Arturo Vidal and Alexis Sanchez a rest following long domestic seasons.
Although a number of key players have been omitted, Chile's second-highest appearance maker Gary Medel is set to feature in the backline on Monday.
Meanwhile, Ben Brereton Diaz is expected to lead the line for La Roja, with the 23-year-old looking to add to the four goals he has already scored for his country.
South Korea possible starting lineup:
Hyeon-woo; Moon-hwan, Kyung-won, Young-gwon, Chul; Woo-young, Paik; Chang-hoon, Woo-yeong, Heung-min; Ui-jo
Chile possible starting lineup:
Perez; Opazo, Diaz, Medel, Mena; Alarcon, Galdames; Montecinos, Parra, Meneses; Brereton Diaz