The Colombians lie third in the standings, but a win would move them up a place with Ecuador not in action tomorrow.
Bolivia have managed just two wins in qualifying so far and sit seventh, but Pekerman insists that is no reason to underestimate them.
"We have to be respectful of Bolivia, they're growing and at a new stage, and I'm sure they will present a tough battle for us," Pekerman said.
Colombia, who will be led in attack by Atletico Madrid star Radamel Falcao, have won three successive matches but Bolivia will also be in confident mood having thrashed Uruguay 4-1 last time out.
Argentina head the standings and take on a Venezuela side currently occupying the fourth and final qualifying spot.
However, Chile and Uruguay are also in the chase for a top-four finish with the three teams all level on 12 points.
Chile visit Peru in the "Pacific Ocean derby" in a match which the home side must also win if they are to retain any hopes of making Brazil next year.
"We know Peru will be aggressive and will look for the victory from the whistle," said Chile goalkeeper Claudio Bravo.
"The first few minutes will be the key, we have to handle that pressure. If we succeed there then we will be able to manage the game."
Uruguay are also in action tomorrow against bottom-placed Paraguay and hoping to turn around their recent slump which has seen them win just once in four matches.
Their current form is a marked difference from that which saw them reach the last four of the 2010 World Cup and win the Copa America a year later, and coach Oscar Tabarez knows the pressure is on.
"We have to beat Paraguay, but preserve our order and balance," he said.
"We can't just go on the attack for no reason.
"If we win this match, then we can go to Chile thinking a draw would be a good result."
The teams will also be in action on Tuesday, when Uruguay visit Chile, Argentina travel to Bolivia, Ecuador host Paraguay and Venezuela face Colombia.