The Ecuadorian arc is composed of an unusually high number of volcanoes, organized as along-arc alignments and across-arc clusters, in a relatively small area. Although several geochronological studies have been carried out in the last three decades, the eruptive history of the central zone of the arc remains poorly documented, preventing analysis of the initiation of volcanism of the whole arc. In this study, we present new K–Ar ages obtained from this central area, referred to as the Quito segment. These results were then incorporated into an updated comprehensive geochronological database of about 250 ages, allowing us to describe, at the arc scale, the spatial and temporal evolution of Quaternary volcanism in Ecuador. About eighty Quaternary volcanoes have been identified in the Ecuadorian Andes, 45 of which have been radioisotopically dated and/or identified as active or potentially active. The volcanic arc developed in three stages, characterized by an increase in the total number of active volcanoes. During the oldest Plio-Early Pleistocene stage, documented volcanic activity was mostly concentrated in the Eastern Cordillera of the Quito segment, with minor effusive eruptions in the southern Back-Arc. Since ~ 1.4 Ma, activity has spread to the surroundings of the Quito segment, and new edifices also appeared in the Western Cordillera and the Inter-Andean Valley. Towards the end of this intermediate stage (i.e., ~ 800 ka), volcanism occurred in isolated areas north and south of the Inter-Andean Valley. Finally, the late and current has been characterized by a remarkable increase in volcanic activity since ~ 600 ka. About 50 volcanoes were active during this stage. The spatial distribution of the Ecuadorian arc volcanism seems to be guided by deep mechanisms (i.e., slab geometry and age, amount and composition (fluids and melts) of slab input, mantle heterogeneities) and old crustal tectonic structures of the Western Cordillera, while neotectonics seems to influence the development of stratovolcanoes. In addition, we note that the spatial and temporal evolution of volcanism highlights the influence of the Carnegie Ridge and the young Nazca crust on the thermal regime of the subduction system, which in turn increases of volcanic activity in Ecuador.