The Madrid striker netted three top-drawer finishes in the perfect start to the Albiceleste's World Cup qualifying campaign.
The Real Madrid striker netted a hat-trick and provided an assist as the ambitious Roja were exposed badly at the back. Lionel Messi also found the net to end his international goal drought, while Matias Fernandez scored what was little more than a consolation for Claudio Borghi's men.
As Alejandro Sabella began his first competitive game at the helm of Argentina, expectations were high from the home crowd at the Monumental. It did not have to wait long to celebrate; a slick counter-attack was capped by a magical cross-field ball from Angel di Maria to Madrid team-mate Gonzalo Higuain, who blasted the ball into the back of the net after just seven minutes.
Despite the early advantage, the Albiceleste did not have everything their own way in the opening exchanges. The home midfield was pressed back by a dynamic Chile outfit, forcing the host to play pensively and from deep. Both Fernandez and Humberto Suazo went close as the Roja pressed for an instant reply.
This angst to attack, however, was bound to have repercussions at the back. Lionel Messi saw a last-ditch tackle from Jean Beausejour rob him of a goal, but seconds later he neatly converted Higuain's through-ball to double the lead and bring some comfort to proceedings.
A rampant Argentina was not satisfied and sewed up the game six minutes into the half with another great finish from Higuain. Jose Sosa foraged down the left before the ball found its way to Di Maria, and a pinpoint cross found 'Pipita' primed to blast home on the run.
Chile then threatened a mini-revival. Eduardo Vargas' cross was only partially cleared by Andujar and the ball eventually ended up with Matias Fernandez to slot home. Hopes of a draw, however, were extremely short-lived.
Messi and Higuain strode forward with little resistance from the Chile backline and a neat one-two left 'Pipita' open to net his third of the evening, provoking a joyous reaction from the usually phlegmatic Sabella.
Argentina travels to Caracas to take on Venezuela next Tuesday, and Chile will hope to bounce back at home to Peru.