With a favourable draw and Barcelona target Alexis Sanchez as the pick of a multi-talented squad, Chile will hope to mount a genuine title challenge in Argentina.
Using the £25 free bet bwin offers new customers to back Paraguay to win the Copa America would return £475 if they land the trophy.
After a disappointing World Cup 2010 qualifying campaign, Colombia are priced at football betting odds of 33/1 by bwin to repeat their 2001 triumph.
Copa America betting fans can back Bolivia to qualify for the quarter-finals at odds of 7/5, although an early exit looks more likely.
With a draw being enough to see both sides through to the second round, odds of 21/10 could attract attention from those using bwin’s free £25 bet.
Los Catrachos are seen as 17/10 outsiders to beat Costa Rica in the first of this year’s Gold Cup quarter-finals.
Luis Milla will send his young side out to win after being held by England and using bwin’s £25 free bet on a win for La Rojita offers potential returns of £39.25.
The host nation will look to keep their winning run going and are priced as 1/5 favourites at bwin to beat Panama.