The hosts might not have as much talent across the board as their South American neighbours, but they will hope that a fervent home crowd can help them to victory.
Not only are La Roja chasing a first Copa title, they have also never won a major international tournament in their history.
They have come close, though. They have hosted the World Cup and Copa America on seven occasions and never not reached the semi-finals on their own turf.
The Chileans have also been runners-up at the Copa on four occasions, the last of which came in 1987 when they fell to Uruguay in the final.
Chile are this year's top scorers with 13 goals in five games and they possess the top marksman in Eduardo Vargas, who has netted four times, including a match-winning brace in the semi-final.
The forward, who was on loan at Queens Park Rangers last season, sealed the win for Chile against Peru with a dipping long-range effort in the 64th minute.
Before that, they had finished top of Group B with two wins and a draw and edged out defending champions Uruguay in the quarter-finals.
Recent Copa America form: WDWWW
Recent form (all competitions): WWDWWW
Like Chile, Argentina drew one game in the group stage to finish top of Group B, setting up a quarter-final with Colombia.
After a goalless 120 minutes, La Albiceleste ousted Los Cafeteros 5-4 on penalties to book a last-four match with surprise package Paraguay, who had toppled Brazil on penalties in the quarters.
La Albiceleste have won the Copa 14 times and victory on Saturday would see them match Uruguay as the competition's most successful ever country.
Their record in Copas hosted in Chile is also superb - they have never failed to reach the final, winning it four times and finishing as runner-up on two occasions.
They are, however, without a major competition win since the 1993 Copa in Ecuador, losing last year's World Cup final to Germany in extra time.
Recent Copa America form: DWWWW
Recent form (all competitions): WDWWWW
Chile, ironically managed by an Argentine in Jorge Sampaoli, could go with the same XI that started against Peru.
Gonzalo Jara remains suspended as he serves the second of a three-game ban, while Stars Claudio Bravo, Arturo Vidal and Alexis Sanchez should be the backbone of the team. Sanchez is a slight doubt and could miss out, but will hope to fight through the pain.
The likes of Carlos Tevez, Gonzalo Higuain and Ezequiel Lavezzi all started on the bench for Argentina in their semi-final win over Paraguay, but former Barcelona boss Gerardo Martino has little reason to change things after the 6-1 demolition of La Albirroja.
Still, a frontline of Di Maria, Sergio Aguero and Messi is not one to be sniffed at.
Chile possible starting lineup:
Bravo; Isla, Medel, Rojas, Albornoz; Diaz, Aranguiz, Vidal; Valdivia; Sanchez, Vargas
Argentina possible starting lineup:
Romero; Zabaleta, Demichelis, Otamendi, Rojo; Biglia, Mascherano, Pastore; Messi, Aguero, Di Maria
Head To Head
Chile have beaten Argentina just once in the two countries' last 14 meetings - a run stretching back to 1959.
Their last encounter was at the same stadium as Saturday's final in qualifying for the 2014 World Cup, and two first-half goals in three minutes from Messi and Gonzalo Higuain were enough for a 2-1 victory.
Neither side has lost a competitive game since their respective World Cup losses at the quarter-final and final stages to Brazil and Germany.
We say: Chile 1-2 (AET) Argentina
Argentina outclassed Paraguay, but it shouldn't be such a walkover against the hosts, who are desperate for their first tournament success. However, Argentina have the magician that is Messi and it's hard to bet against the scampering genius. A draw in 90 minutes is likely, but we're backing La Albiceleste to edge extra time to equal Uruguay's Copa record of 15 wins.