Brazil were undone by a slice of magical talent on Wednesday as they fell 0-2 to Mexico in their first competitive match under coach Dunga.
Nery Castillo set Mexico on their way with a goal any Brazilian player would have been proud of, before Ramon Morales curled in a 30-metre free-kick.
Chile twice came from behind and then scored a late winner to beat Ecuador 3-2 as drama dominated day two of the tournament.
The competition began with Peru stunning Uruguay 3-0 and Bolivia twice coming from behind to hold hosts Venezuela 2-2 on Tuesday.
Mexico had arrived under the shadow of Sunday's 2-1 defeat by the United States in the Concacaf Gold Cup final, without several key players and amid reports of rifts in the squad.
Defending champions Brazil, on the other hand, were raring to go. They had played only friendlies since Dunga took over in August, losing once in nine outings.
Mexico went ahead in the 21st minute through Castillo. Latching onto Juan Carlos Cacho's chip into the area, the Olympiakos striker flicked the ball over Juan and then past goalkeeper Doni without letting it touch the ground in the 21st minute.

Successive win
Morales’ free-kick eight minutes later gave Mexico their second successive win over Brazil following their 1-0 victory at the Confederations Cup two years ago.
Brazil took control of the game in the second half but were foiled by goalkeeper Guillermo Ochoa, the crossbar and defender Fausto Pinto, who cleared one chance off the line.
With the last move of the game, Castillo broke away, ran half the length of the pitch, rounded Doni and then shot wide of the open goal. The game was preceded by a five-goal thriller in which Luis Antonio Valencia and Cristian Benitez twice put Ecuador in front, only for Humberto Suazo to equalise each time.
Ecuador were twice denied by Claudio Bravo while leading 2-1 and paid heavily when substitute Carlos Villanueva curled in an 87th minute free-kick.
The tournament continues on Thursday with a Group C double bill in Maracaibo. Paraguay face Colombia in the opening match, then favourites Argentina meet the United States.