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.
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.
Chile took control of the shoot-out when Gonzalo Higuain blazed his penalty over the bar before Chile goalkeeper Claudio Bravo saved Ever Banega’s spot-kick.
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.
The four-time world footballer of the year had repeatedly spoken of his desperation to win a title with Argentina after winning everything at club level with Barcelona.
But the 28-year-old superstar was to suffer more disappointment, only 12 months after enduring another agonising extra-time defeat in last year’s World Cup final against Germany in Brazil.
Chile’s win was their first ever victory over Argentina in the Copa America.
– ‘Dream come true’ –
“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’s Argentina-born coach Jorge Sampaoli said his side had deserved to win.
“We had to play a great game against one of the world’s best teams for the quality of players,” Sampaoli said.
“We should have won in 90 minutes, but ended up getting justice.”
Argentina’s players meanwhile were left pondering another heartbreaking loss.
Midfielder Javier Mascherano has now played in three losing Argentina teams in Copa America finals, and was also a member of the team beaten in the World Cup final.
“Three Copa America finals, three defeats … I can’t explain the losing streak,” a dejected Mascherano said.
“We just didn’t seem to have that little bit of luck that you sometimes need to have to win in finals. Is it karma? I don’t know.”
Argentina coach Gerardo Martino meanwhile lamented his side’s failure to take chances.
“They were very clear chances that should have changed the outcome of the game,” Martino said.
Earlier, Chile had begun the final at a ferocious pace before Argentina gradually managed to gain a foothold in the game.
While Chile pressed forward relentlessly and launched a series of forays into Argentinian territory, it was the tournament favourites who had the better chances in the first half.
Argentina almost grabbed an opener in the 20th minute when Sergio Aguero met a Messi free-kick with a close range header that Bravo parried away.
On the stroke of half-time Argentina probed again and Javier Pastore set up Ezequiel Lavezzi whose shot was blocked by Bravo.
The second half followed a similar pattern, with clear-cut chances thin on the ground as defences remained on top.
Sanchez went close for Chile on 82 minutes but hooked his volley just wide of the post.
Argentina almost snatched a dramatic victory in the dying seconds with a well-worked move that began after Messi skipped clear of the Chile defence and released Lavezzi on the left flank.
Lavezzi found Higuain — on for Aguero — at the far post but the Napoli striker couldn’t finish from a tight angle and shot into the side netting as Chile escaped.
In extra-time Sanchez almost punished a rare slip by Mascherano but shot over the bar.
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