 He then volunteered for the missions of New Spain

Piccolo arrived in the Americas in 1684, when he went on to serve as a Jesuit missionary for 13 years among the Tarahumara of Chihuahua before being assigned to the new Baja California mission field.During this period, in 1689, he made his final religious profession as a member of the Society.Eusebio Francisco Kino, S.J., the original driving force behind the Jesuit effort who had made two unsuccessful attempts at establishing a mission, was unable to participate when his project finally became a reality.