Monday's draw for South American football's premier continental competition saw Colombia placed alongside Brazil, Peru and Venezuela in Group C.
Colombia were famously beaten 2-1 by Brazil in the World Cup quarter-final earlier this year in a game best remembered for the controversy surrounding Juan Camilo Zuniga's challenge on Neymar, which ruled the Barcelona star out of the rest of the tournament with a fractured vertebra.
But Pekerman feels his team are capable of turning the tables on Dunga's side when they meet in Chile in June 2015.
"We knew we were going to face one of the big teams of South America in the group stage, the top seeds," Pekerman said after the draw in Vina del Mar.
"We get Brazil again - as always, it is a positive, because it is an opponent we know very well.
"They are in another process [Dunga took over from Luiz Felipe Scolari following the World Cup], we just played a friendly match [Brazil beat Colombia 1-0 in Miami back in September] and they are now in an important streak with a new project.
"It's still early in its journey, so we will see how to face them after our first game. It will be a crucial game that will define our championship.
"Hopefully [we can beat Brazil] - we want to do it. We know the strengths they have, but we will prepare well.
"We will take advantage of past experiences. We know it is a difficult game, but we have to fight a lot to get that win."
Dunga's assistant coach Andrei, meanwhile, has targeted the regaining of the Copa America title that Brazil last won in 2007.
"In a competition like [the] Copa America, Brazil has to play looking for the title of the competition," he explained.
"Like any other competition, Brazil has to play and struggle for the title."