E. Rossoni places this surname in the Milan area and proposes that it would derive from a nickname: either because the first bearer was in the service of a family that had had a captain among its members, or because he was distinguished by a behaviour of an authoritarian character.

This surname —of late appearance— would derive from an older noble predicate that was lost over time. As examples there are cited the Capitani of Bregnano —who later came to be called Carcano—, those of Asnago and those of Cermenate, cases in which the locality of origin disappeared from the surname. The inverse process is illustrated by the Parravicino, originally Capitanei de Paravixino, who ended up adopting only the toponymic denomination.

In 1690, Pirro De Capitani received the investiture of the fief of Concorrezzo; in 1691, King Charles II granted him the title of count; and in 1737, the emperor Charles VI granted Count Pirro de Capitani the honours corresponding to the Grandees of Spain. In Concorrezzo a Baroque-style palace known as "Palazzo dei Capitani di Scalve" is preserved.