Defending Copa America champs Chile kicked off their 2018 World Cup qualifying campaign by sinking Brazil 2-0 in Santiago.
Eduardo Vargas’ side-footed volley and Alexis Sanchez’s 90th minute goal secured the points for the hosts.
It was Brazil’s first World Cup qualifier in six years.
Neymar was not in the team as he is still serving his four-game international suspension.
A Messi-less Argentina were forced to cope with the early exit of Sergio Aguero, and were defeated 2-0 by Ecuador in Buenos Aires.
Goals from Frickson Erazo and Felipe Caicedo ensured that the Ecuadorians enjoyed a famous victory at the Estadio Monumental.
An Uruguay side without suspended duo of Luis Suarez and Edinson Cavani defeated 10-man Bolivia 2-0 in La Paz.
Uruguay were always in control and led in the 10th minute when Martin Caceres fired home a loose ball from close range.
Skipper Diego Godin made the game safe with 21 minutes remaining when he headed home Carlos Sanchez’s cross to double the lead.
It was Colombia’s first ever away win in Bolivia.
The hosts were reduced to 10 men after Jair Torrico saw red for two yellow cards.
Colombia also got off to a winning start as they beat Peru 2-0 in Barranquilla.
Teofilo Gutierrez put them in front nine minutes before the break as he converted from a corner and the game was put to bed at the death as Edwin Cardona fired in a second from a quick counter attack.
Paraguay left it late to beat Venezuela as they triumphed 1-0.
A stalemate looked on the cards until Derlis Gonzalez popped up with the winner in the 85th minute.
Bolivia 0 – 2 Uruguay
Colombia 2 – 0 Peru
Venezuela 0 – 1 Paraguay
Chile 2 – 0 Brazil
Argentina 0 – 2 Ecuador