With heavily-fancied sides Argentina and Uruguay both sharing the group, these two teams will likely find themselves battling with each other and Chile for the final two qualification spots if they are to reach the quarter-finals, making the opening game crucial.
Paraguay come into the tournament in a four-game winless run, most recently losing 2-0 to Brazil in World Cup Qualifying action earlier in June.
While that did make it four games without a win for Eduardo Berizzo's side, their three previous results were draws, including commendable results against Uruguay and Argentina.
Their other draw came against Tuesday's opponents in the qualifying group in November, as Alejandro Romero equalised after Bolivia led through Marcelo Moreno and Boris Cespedes to see the game finish 2-2.
Their run of frequent draws means that La Albirroja sit in sixth spot in their World Cup Qualifying group, having collected seven points from their first six games.
However, they will firmly turn their attention to the Copa America for now, as Paraguay look to build on their two previous titles, with their most recent triumph coming in 1979.
They take on a Bolivia side who are yet to lift the continental trophy, and will also be in competition for spots in the top four to book their spot in the quarter-finals.
Bolivia come into the tournament having only qualified out of the Copa America group stage once since the turn of the century.
That appearance came in 2015, as they came second in their group before suffering a 3-1 defeat to Peru in the quarter-final.
However, they will come into the 2021 edition with a renewed sense of optimism, having recently improved their form in World Cup Qualifying.
After a poor start to the group with three consecutive defeats, Cesar Farias's side have since gone three qualifying games without a loss, collecting five points from those matches.
They started with that 2-2 draw against Paraguay, before a Marcelo Moreno brace and a Diego Bejarano goal fired the Greens to a 3-1 win over Venezuela.
Most recently, Farias's men picked up another point in a commendable 1-1 draw with Chile, as Moreno equalised from the penalty spot in the 82nd minute after Erick Pulgar had put the hosts ahead.
That upturn in form saw them move up to eighth spot in the group, while they can continue that rise if they are able to sustain their improvement.
For now, they will look to carry that momentum into Tuesday's opening game against one of their biggest competitors, before they face unenviable clashes with Argentina and Uruguay.
The Paraguay line should be led by Angel Romero, who has six goals in 24 appearances for his nation.
He will be complemented by Paraguay's key man Miguel Almiron, who has made himself a crucial cog for Newcastle United with consistent performances behind the front line.
Bolivia will be led by talisman Marcelo Moreno, who has starred on the international stage for over 10 years with 25 goals in 83 appearances.
He will come in with plenty of confidence, having netted six goals in his last six caps to move clear as the nation's all-time top scorer.
Always Ready midfielder Juan Carlos Arce also brings plenty of experience, having featured 76 times in a Bolivia shirt, netting an impressive tally of 12 goals in that time from midfield.
Paraguay possible starting lineup:
Silva; Rojas, Gomez, Balbuena, Alonso, Arzamendia; Villasanti, Gimenez, Cardozo Lucena; Romero, Almiron
Bolivia possible starting lineup:
Lampe; Diego Bejarano, Haquin, Jusino, Sagredo; Arce, Justiniano, Danny Bejarano, Cespedes, Ramallo; Moreno
We say: Paraguay 2-1 Bolivia
In what will be a crucial game in deciding who takes pole position to qualify for the final eight, we see Paraguay having the narrow edge on Tuesday.
While Moreno poses a major threat, La Albirroja possess quality all over the pitch, and they should have enough to get over the line.
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