The Chile legend scored 34 goals in 69 appearances for his national side but failed to deliver an elusive victory in the South American showpiece.
Alongside Marcelo Salas, Zamorano was one of Chile's best players during an international career that lasted 20 years, with the nation now back among the best teams on the continent following a strong showing at the World Cup.
Talents such as Alexis Sanchez, Arturo Vidal and Claudio Bravo helped Jorge Sampaoli's side to the last 16 where they exited at the hands of hosts Brazil.
However, ahead of the tournament in June and July, Zamorano backed the national side to deliver.
"The expectations are high because of this generation," he told the competition's official website.
"Today we have a great generation of players, and they really want to achieve something important for the country.
"I see a big chance when a lot of Chile’s players are with the most important teams of the world.
"That has never happened. There always have been two or three players in the most important leagues, but not now.
"This team has the experience to do it."
During the Copa America era, Chile have finished runners-up twice - to Paraguay in 1979 and Uruguay in 1987.
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