The first half ended scoreless at the Estadio San Carlos de Apoquindo, however, Martin Lasarte's Catolica broke the game open when Jose Munoz was on target five minutes after the interval.
Quick-fire goals from Ismael Sosa (69th minute) and Nicolas Castillo (73rd) then iced the points for the home side, who sit top of the table with 14 points from six matches.
Cobreloa sit second and are the only other unbeaten team so far this season after a 2-1 home win over Rangers.
Gaston Lezcano broke the deadlock in the 72nd minute, after Jonathan Chaves' penalty for Cobreloa was cancelled out by a strike from Rangers' Pablo Vegetti.
O'Higgins fall to fourth spot, after a 1-0 home loss to Palestino, with Universidad de Chile climbing above them on goal difference courtesy of their 2-2 home draw with Santiago Wanderers.
Union Espanola won their second match of the term, accruing a 2-0 win away at Colo Colo, while Deportes Iquique were held to a 1-1 stalemate at home to Huachipato.
Universidad de Concepcion earned a point at the death, equalising in the fifth minute of injury time via Jose Luiz Jimenez for a 2-2 stalemate against Nublense.
Antofagasta got the jump on Everton with an early goal and consolidated for a 2-0 victory, while Union La Calera were held to a 1-1 draw at home to Audax Italiano.
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