Arsenal star Alexis Sanchez struck the winning spot-kick for Chile, as the hosts clinched a 4-1 shoot-out victory when the game ended goalless after extra time yesterday.
Messi's Barcelona teammate, goalkeeper Claudio Bravo, was the real star was Chile. Bravo stopped Ever Banega's low shot by diving to his left to make the save, and earlier Gonzalo Higuain also missed for Argentina, sending his shot over the crossbar. The Chileans made all of their penalties.
Sanchez chipped the decisive penalty down the middle past Sergio Romero to spark wild celebrations in front of a 45,000 capacity crowd at the Estadio Nacional in Santiago.
Argentina captain Messi, aiming to inspire the South American giants to a first international title in 22 years, could only look on distraught as Chile celebrated. Chile's win was their first ever victory over Argentina in the Copa America.
"It is a dream come true. We have worked so hard for this," said Chile star Arturo Vidal. The midfielder said Chile had been determined to win the Copa America after exiting the World Cup last year on penalties.
"We talked about it in Brazil that we were going to win the Copa America," Sanchez said. "This is really a great generation we deserve this."
Chile started at a ferocious pace before Argentina gradually managed to gain a foothold in the game.
Messi, invariably tracked by two or three red jerseys throughout, almost played Sergio Aguero in with a superb pass after six minutes only for Chile to clear.
At the other end Chile came closest to opening the scoring early on when Vidal volleyed a deflected Sanchez cross goalwards, with Romero diving to save.
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