Exposures of the Earth’s crust-mantle transition are scarce, thus, limiting our knowledge about the formation of subcontinental underplate cumulates, and their significance for metal storage and migration. Here, we investigated chalcophile metals to track sulfide crystallization within the Contact Series, an <150-m-thick pyroxenite-gabbronorite sequence, formed by mantle-derived melts, highlighting the boundary between the Balmuccia mantle peridotite and gabbronoritic Mafic Complex of the Ivrea-Verbano Zone. Within the Contact Series, numerous sulfides crystallized in response to the differentiation of mantle-derived underplated melts. Such sulfide-controlled metal differentiation resulted in anomalous Cu contents (up to ~380 ppm), compared to reference mantle (~19 ppm) and crustal samples (~1 ppm). We propose that the assimilation of continental crust material is a critical mechanism driving sulfide segregation and sulfide-controlled metal storage. Our results evidence that sulfides are trapped in the underplated mafic-ultramafic cumulates and that their enrichment in Cu may provide essential implications for crustal metallogeny.