The mineralization potential of arc magmas depends, among other factors, on the timing of sulfide melt saturation relative to magma differentiation and to exsolution of a magmatic fluid phase. In fossil mineralized or barren systems, understanding the evolution of metals along the magma differentiation path is often hindered by late magmatic processes and hydrothermal alteration. To better understand the process of metal evolution “caught in the act” in crustal reservoirs, we analyzed magmatic sulfides and melt inclusions found within eruptive products from the active arc volcano, La Fossa (Vulcano Island, Italy), for the basalt to rhyolite compositional spectrum. We found that, in case of sulfide-undersaturated and volatile-rich arc basalts, metals are scarcely subtracted by degassing during ascent to shallowcrustal reservoirs and reach the highest abundances in intermediate magmas (250 ppm Cu). At sulfide saturation the sulfide melt has 34–66 wt% Cu, leading to a dramatic decrease in chalcophile metals dissolved in the silicate melt. After fractionation of only 0.2–0.3 wt% of sulfide in the solid assemblage, the exsolved sulfide is a monosulfide solid solution (pyrrhotite) containing <3 wt% Cu. Metals that do not partition in sulfides (Pb, Zn) increase their concentrations during magmatic evolution until they are sequestered by a Cl-rich aqueous fluid phase exsolved at the rhyolitic stage. The absolute and Cu-normalized concentrations of metals in sulfide inclusions are similar to sulfide accessories in magmatic rocks associated with world-class porphyry Cu systems. Our results demonstrate that the mechanisms governing metal evolution inferred for the magmatic stage in porphyry Cu environments can be also tracked at an active arc volcano, using eruptive products as snapshots of the magmatic evolution. Arc volcanoes can thus be viewed as ideal active analogues when studying these crucial processes for the formation of porphyry Cu deposits.