Independiente, playing in South America's elite club competition for the first time since 2004 and facing a long haul if they are to reach their eighth final in June, went ahead with a 50th-minute debut goal by new signing Matias Defederico.
The Reds, from the Buenos Aires suburb of Avellaneda, who won the last of their seven titles in 1984, are the biggest name in the six preliminary round ties, which also includes Brazilian big guns Corinthians, still looking for their first crown.
Independiente, who have struggled in the domestic league, qualified for the competition by winning last year's second-tier Copa Sudamericana and reinforced their team bringing Defederico home from Corinthians.
Defederico pounced on a poor clearance of Andres Silvera's left cross to open the scoring with a left-footed shot and substitute Patricio Rodriguez netted the second in the 70th minute from Nicolas Cabrera's free-kick.
"I'm confident we will go through. It's a good difference (of two goals) and we must make sure we defend it," midfielder Roberto Battion said looking ahead to the second leg in Quito next week.
GROUP PHASE
The group phase starts in two week's time when holders Internacional of Brazil take their bow away to Ecuador's Emelec in the Pacific port city of Guayaquil in Group Six on February 16 bidding for a third title after first triumphing in 2006.
In Group Seven, Argentine champions Estudiantes face Cruzeiro on February 16 for the first time since meeting the Brazilian side in the 2009 final which they won to lift their fourth title.
Group Three appears to be the toughest with Brazilian champions Fluminense, three-times winners Nacional of Uruguay, 1985 champions Argentinos Juniors of Argentina and Mexican giants America. Flu are at home to Argentinos in Rio de Janeiro in their opening match on February 9.
Argentina's Boca Juniors, who won the trophy four times between 2000 and 2007 and six times overall, are notable absentees along with their arch-rivals River Plate, twice winners who have also fallen on hard times.
If Independiente win their tie, they will go into Group Eight and meet Uruguayan five-times champions Penarol at home in their February 24 opener, a clash steeped in Libertadores Cup tradition.
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