The Juventus midfielder struck from the spot and substitute Vargas made sure of the 2-0 opening-day win for the hosts against Ecuador.
Chile's bid to win a maiden Copa America title got off to the perfect start after the host nation powered past Group A rivals Ecuador 2-0 in Santiago.
Arturo Vidal broke the deadlock via a 67th-minute penalty and substitute Eduardo Vargas sealed the points with six minutes remaining in the Copa opener at the Estadio Nacional on Thursday.
Vidal stepped up and converted his own spot-kick after he was fouled by Ecuador forward Miller Bolanos, before Vargas came off the bench - replacing Jean Beausejour at half-time - and put the result beyond doubt late on in the Chilean capital.
Jorge Sampaoli made three changes to the team that beat El Salvador 1-0 in their final Copa America warm-up, with captain Claudio Bravo, Vidal and Eugenio Mena drafted into the line-up at the expense of Johnny Herrera, Felipe Gutierrez and Vargas.
Ecuador were unchanged, with Gustavo Quinteros opting to stick with the same XI that routed Panama 4-0 in a friendly last week.
Chile were by far the more superior team in the first half, but had nothing to show for their efforts.
The host nation dominated from the outset and Alexis Sanchez - a constant threat - came close to breaking the deadlock early on but his attempted chip failed to deceive onrushing goalkeeper Alexander Dominguez.
Bravo was forced into a save by Fidel Martinez not long after, when Jorge Valdivia played Chile into trouble with a short free-kick just outside the penalty area.
Chile continued to dictate proceedings, howver, with Vidal the architect in the middle of the pitch, but try as they might there was no goal before the break, despite opportunities falling to Sanchez and Mauricio Isla.
It was a similar story in the second half, Sanchez leading the charge up front, though it yielded no reward for Chile.
In a rare foray in the attacking third, Ecuador came close to opening the scoring after 53 minutes but Enner Valencia was unable to direct his shot on target.
Ecuador's defence was finally breached just after the hour mark, albeit from the penalty spot.
Bolanos brought down Vidal with an arm across his chest and the Juventus midfielder made no mistake, firing the ball into the top corner of the net.
Ecuador were unlucky not to snatch a point after Valencia's header cannoned off the crossbar with nine minutes remaining.
And Chile went up the other end and sealed the points two minutes later, when Vargas curled the ball underneath Dominguez, having been played in by Sanchez.
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