Argntina's Boca Juniors also enter the fray along with three other Brazilian sides as the group stage enters its second week in the South American equivalent of the Champions League.
After providing both teams for the 2005 and 2006 finals, Brazil will be hoping to reassert their dominance which has slipped in the last two years when Boca and then LDU won the title.
Palmeiras, under irrepressible former Brazil and Real Madrid coach Luxemburgo, appear to offer Brazil's strongest challenge and should give LDU the toughest possible start to the defence of their crown.
Inspired by new signing Keirrison in attack, Palmeiras have won their first nine games of the 2009 season -- seven in the Paulista championship and both legs of their Libertadores preliminary round tie.
Luxemburgo has already announced that he will recall Marcos, Brazil's 2002 World Cup winning goalkeeper, for the Group One match at 2,800 metres above sea level in Quito. Marcos has been suffering from a thigh injury.
Luxemburgo has won the Brazilian championship a record five times along with numerous regional tournaments but the Libertadores has so far eluded him.
LDU, the first Ecuadorean team to win the Libertadores, have lost forwards Luis Bolanos and Joffre Guerron from last year's side while Edgardo Bauza has been replaced by former Uruguay and Qatar coach Jorge Fossati.
Chilean champions Colo Colo and Brazilians Sport Recife, who meet in Santiago on Wednesday, complete arguably the toughest of the eight groups.
"It's not the group of death," said Luxemburgo dismissively. "We know we have tough opponents in front of us but Palmeiras are good enough to qualify."
Two more Brazilian teams have home matches this week with Sao Paulo facing Colombia's Independiente Medellin in Group Four on Wednesday and Cruzeiro entertaining Argentine's Estudiantes in Group Five on Thursday.
Estudiantes are hoping influential midfielder Juan Sebastian Veron will have recovered from injury for the match in Belo Horizonte.
Boca Juniors, who have won the tournament four times since 2000 and six overall, host Ecuador's Deportivo Quito in a Group Two match on Tuesday.
