The Quaternary Nevado de Longaví volcano of the Andean Southern Volcanic Zone (SVZ) has erupted magmas that range in composition from basalt to low-silica dacite, although andesites are the dominant erupted magma type. Amphibole is a common phenocryst phase in andesites throughout the volcano, and it is the dominant mafic phase in Holocene dacites and their included mafic enclaves. Compositions of magmas erupted at Longaví volcano define arrays that diverge from trends delineated by neighboring frontal-arc volcanoes. Although mafic compositions at Longaví are broadly similar to basalts at other SVZ centers, Longaví intermediate and evolved magmas have systematically lower abundances of incompatible major (K2O, P2O5) and trace elements (Rb, Zr, Nb, REE, Th, etc), as well as high Ba/Th, Sr/Y, and La/Yb ratios. Longaví volcano magmas define two differentiation series with regard to enrichments of Rb (and other incompatible elements) with increasing silica. A high-Rb series that includes the oldest units of the volcano comprises basalts to andesites dominated by anhydrous mineral assemblages with chemical compositions similar to other SVZ magmatic series. The series with low Rb, on the other hand, includes the Holocene units that evolved from basaltic andesites to dacites by means of fractional crystallization wherein amphibole and calcic plagioclase dominate the mineral assemblage. Magmas parental to low-Rb series are interpreted to be high-degree mantle melts, highly hydrous and oxidized, formed as a response to high fluid inputs into the subarc mantle. Enhanced water transport to the subarc mantle is a plausible effect of the subduction of the oceanic Mocha Fracture Zone that projects beneath Nevado de Longaví. Volcanoes located over oceanic fracture zones further south along the SVZ have erupted hornblende-bearing magmas that share some chemical similarities with Longaví volcano magmas.