Catolica journeyed to bottom side Deportivo Quevedo and had goals from Federico Laurito and Diego Benitez to thank for their triumph.
Emelec, meanwhile, defeated LDU Loja 2-0 thanks to goals from Gabriel Achilier and Fernando Gaibor, the latter from the penalty spot.
Both Emelec and Catolica have won their first three matches of the new season and have a goal difference of plus-seven.
Manta moved into third place via their 1-0 victory over Macara, with a 90th-minute goal from Luis Escalada the difference between the two sides.
Deportivo Quito enjoyed a 1-0 win over Independiente, while El Nacional won by the same scoreline against LDU Quito.
And Barcelona had a 71st-minute equaliser from Cristian Penilla to thank for their 3-3 draw at home against Deportivo Cuenca.
Andres Rios scored a brace for Cuenca, and when the 24-year-old Argentine netted his second just before the half-time his side were up 3-2.
But Pernilla's goal with 20 minutes remaining ensured honours remained even between the two strugglers, with neither side breaking their winning duck this season.