Neither of these sides have previously won the tournament, but much is expected of the Chileans in particular, with the bookmakers having installed them as third favourites to triumph behind South American giants Brazil and Argentina.
Much of the credit for that should go to head coach Jorge Sampaoli, who since taking charge in 2012 has implemented a new playing style.
The 55-year-old Argentine demands that his side play with a high tempo and push their opposition further up the pitch.
It is a strategy that has won La Roja many admirers, particularly at last summer's World Cup where they showed that they had the ability to mix it with the very biggest nations. Holders Spain were defeated in the group stages, while they were unfortunate not to knock Brazil out in the last 16.
Since those exploits, their form in friendlies has been patchy, with three defeats having been suffered in their last five outings.
Nevertheless, with the likes of Claudio Bravo, Gary Medel, Arturo Vidal and Alexis Sanchez all fit and primed for action following impressive seasons for their respective club sides, Sampaoli's men are expected to go deep in the competition.
It is a tournament that they have never previously won, but, playing in front of a passionate home crowd, this perhaps represents Chile's best opportunity to be crowned South American champions.
Recent form: DLWDWL
Recent form (all competitions): WLWLLW
The Ecuadorians will have fancied their chances of progressing through a group that contained France, Switzerland and Honduras at last summer's World Cup, but despite holding the French to a credible draw, they ended up in third spot and were eliminated.
Head coach Reinaldo Rueda paid the price for that when he was relieved of his duties soon after, and while Sixto Vizuete had a brief stint in interim charge, the role of restoring pride in the team has been handed to Gustavo Quinteros.
Like his compatriot Sampaoli in the opposite dugout, the 50-year-old has a wide variety of managerial experience from his stints in charge of numerous South American clubs.
However, if Ecuador's recent Copa America history is anything to go by, Quinteros has a tough job on his hands. Heading into the tournament, La Tri are without a victory since a 4-0 win over Venezuela in 2001, which is a total of nine matches.
Going further back, since entering the 1995 instalment of the competition, there have been just four victories from 22 outings, during which there were 16 defeats inflicted.
However, there have at least been signs of late that Quinteros has made the North-Western country a more competitive force, with two wins and a draw being picked up from their last five friendly encounters.
Recent form: LLLDLL
Recent form (all competitions): DWLLDW
As for Chile, a check will be made on Vidal following his outing on Saturday night for Juventus in the Champions League final. The industrious midfielder was not in top condition for the World Cup, so he is likely to shake off any fatigue to play.
Injuries have sidelined striker Esteban Paredes and midfielder Carlos Carmona for the entire tournament, while former Liverpool winger Mark Gonzalez was overlooked by Sampaoli, despite the fact that he is a veteran of 51 caps.
Chile possible starting lineup:
Bravo; Silva, Medel, Jara; Isla, Beausejour, Aranguiz, Mena, Vidal; Vargas, Sanchez
Ecuador possible starting lineup:
Dominguez; Paredes, Ayovi, Mina, Achilier; Martinez, Noboa, Lastra, Bolanos, Montero; Valencia
Head To Head
In total, there have been 50 previous meetings between these two nations, with Chile the clear leaders thanks to their 27 victories.
As for Ecuador, they have won on 10 occasions, the most recent of which was achieved in October 2012.
They last faced each other in the Copa America back in in 2007 when a brace from Humberto Suazo helped to seal a 3-2 victory for the Chileans.
We say: Chile 2-0 Ecuador
Chile will have the expectation of a nation on their shoulders, but with the quality at their disposal, they should be able to deal with that against Ecuador. Opening matches of a tournament can be tight affairs, but a routine win for Chile is widely anticipated.