Gonzalo Higuain scored a hat-trick and created a goal for Lionel Messi as Argentina beat Chile 4-1.
Higuain started because of injury to Sergio Aguero and took full advantage, opening the scoring in the ninth minute.
Real Madrid team-mate Angel Di Maria sent in a long pass from the left which Higuain controlled and shot past goalkeeper Claudio Bravo.
Higuain then turned provider in the 25th minute when he received the ball from Jose Sosa and sent the ball into the box to find Messi who doubled the advantage.
Following the half-time break, Higuain put Argentina 3-0 up when he converted Di Maria's cross from the left.
Chile pulled one back when goalkeeper Mariano Andujar failed to clear the ball and Matias Fernandez pounced to reduce the deficit to two goals.
However, Higuain hit back three minutes later when Messi intercepted Bravo's clearance and combined with the Real Madrid striker who completed his hat-trick.
Uruguay got off to an ideal start as they opened their 2014 World Cup qualifying campaign with a 4-2 win over Bolivia.
Uruguay reached the semi-finals of last year's World Cup in South Africa and won the Copa America two months ago to become one of the top countries in the region.
They almost went ahead in the first minute when Maximiliano Pereira almost opened the scoring and just two minutes later they did go ahead through Luis Suarez who pounced on a loose ball following a corner.
Bolivia though hit back and Rudy Cardozo levelled in the 17th minute before Uruguay regained the lead eight minutes later when Diego Lugano headed home Diego Forlan's cross.
An Edinson Cavani header nine minutes afterwards gave Uruguay a two-goal lead.
Lugano pounced on indecision by the Bolivia defence from Forlan's free-kick to score the fourth in the 71st minute before Marcelo Martins reduced the arrears towards the end with a penalty.
"The result is the less important thing here. What has real value is that we were clearly superior to our rivals. The only negative issue is that we missed too many goals," Uruguay boss Oscar Tabarez said.
"I'm very satisfied with the players' performance. We tried to play as we always do, in the rivals' field and feeding the forwards. It went very well."
Meanwhile, Paolo Guerrero scored twice to give Peru a 2-0 win at home to Paraguay.
There was nothing to choose between the sides at the start, with both teams concentrating on defence.
Peru were on top by the end of the first half with Paolo Guerrero and Claudio Pizarro both having efforts.
They took the lead a minute after the break when Guerrero took on the goalkeeper Diego Barret to open the scoring.
In the 72nd minute, Pizarro crossed and Guerrero slotted home to seal the victory.
Ecuador beat Venezuela 2-0 thanks to goals by Jaime Ayovi and Christian Benitez in Quito.
The hosts were on top from the start and they opened the scoring in the 14th minute when Antonio Valencia crossed for Benitez whose header came back off the bar but Ayovi pounced on the rebound and headed home.
They doubled the lead in the 27th minute, Valencia played the ball in from the right which Benitez headed into the net.
"We scored in the perfect time, and then we just had to control the game," said Ecuador's Colombian coach Reinaldo Rueda. "It would have been nice to score more, we had like 14 goal chances, but anyway was a nice victory.
"This is a young team, with a very promising future in the qualifiers. If we keep the balance we will become stronger."