Colombia come into the tournament heavily fancied to qualify out of their group, while Ecuador may find themselves in a battle with Peru and Venezuela for two spots, with a win on Monday giving them a huge platform.
Colombia should come into this tournament with some momentum, having picked up positive results in their first two games of the year at the beginning of June.
They then defied the odds to snatch a point with a 2-2 draw at home to Argentina, despite the visitors leading 2-0 after 10 minutes.
Luis Muriel pulled a goal back for Colombia from the penalty spot soon after half time, but they still looked set to fall to a defeat until Cristian Borja netted a dramatic equaliser in the 94th minute to earn a point for his side in qualifying.
Despite an inconsistent start to the qualification campaign, with two wins, two draws and two defeats from their opening six games, Rueda's men still sit comfortably in fifth spot, and could quickly move up if they continue their upturn in form.
For now, they will focus their attention on the Copa America, as La Tricolor look to regain the trophy that they won for the first time in 2001, with the hopes of kicking the group campaign off with a win on Monday.
They take on an Ecuador side who will also be desperate to start with a victory, as they could find themselves in a heated battle to reach the final eight.
Having previously had a strong start to their World Cup Qualifying bid, Ecuador come into this tournament on the back of consecutive defeats, firstly losing 2-0 to Brazil.
Gustavo Alfaro's side did well to hold the defending Copa America champions for over an hour, but Richarlison eventually broke the deadlock in the 65th minute before Neymar added a second goal deep into added time from the penalty spot.
They then suffered a more concerning defeat, as Alfaro's men were beaten 2-1 by Peru, with Gonzalo Plata's injury-time goal unable to spark a full comeback after Christian Cueva and Luis Advincula had given their opponents a two-goal lead.
With intense competition for places in the quarter-finals, Ecuador will look to start their Copa America campaign with a win to put those recent defeats behind them and take a huge step closer to making the final eight.
Colombia come into the tournament without talisman James Rodriguez, who has been omitted due to fitness concerns.
They still boast a fairly strong midfield though, with Porto duo Mateus Uribe and Luis Diaz offering plenty going forward while combative Al-Hilal man Gustavo Cuellar will shield the back four.
The attacking line should be led by Atalanta pair Luis Muriel and Duvan Zapata, having registered a combined 37 goals and 19 assists in the Italian top flight, inspiring their side to a third-placed finish.
Tottenham Hotspur centre-back Davinson Sanchez and Everton defender Yerry Mina should continue their established pairing at the heart of the back four, shielding Napoli goalkeeper David Ospina between the sticks.
Enner Valencia should return to the Ecuador side to lead the line, as he goes in search of a goal to make him the sole top scorer in his nation's history.
Winger Gonzalo Plata will also hope that his goal off the bench last time out is enough to earn him a starting spot for the opening Copa America game.
Exciting Brighton and Hove Albion prospect Moises Caicedo will feature in the midfield, offering plenty of threat going forward.
Colombia possible starting lineup:
Ospina; Medina, Mina, Sanchez, Tesillo; Cuadrado, Uribe, Cuellar, Diaz; Zapata, Muriel
Ecuador possible starting lineup:
Dominguez; Perlaza, Arboleda, Arreaga, Estupinan; Plata, Mendez, Caicedo, Carabali; Estrada, Valencia
We say: Colombia 2-0 Ecuador
While this could be a cagey low-scoring affair as both sides look to settle in for the tournament, we see Colombia having too much quality for their opponents and finding a way to win as a result.
Rueda's men come in with high expectations of success, and they should kick off their campaign with a victory to establish themselves at the top end of the group.