Magmatic Ni-Cu-platinum group element (PGE) deposits are commonly located in tectonically active regions that typically undergo significant deformation and metamorphism and subsequent reworking of sulfide. The Munali Ni deposit is hosted by a dynamic intrusive mafic-ultramafic system situated within the Zambezi belt in southern Zambia. The deposit comprises Fe-Ni–dominant magmatic sulfides, present as a number of lenticular massive sulfide bodies that display a variety of magmatic and metamorphic sulfide textures. The sulfide lenses are uniformly deficient in iridium subgroup PGEs (IPGEs), Au, and Cu, with unusual but characteristically high bulk Ni/Cu ratios (~10) and a consistent precious metal mineral assemblage dominated by Pd and Pt tellurides. On a centimeter to meter scale, Cu tenors and Ni/Cu ratios are extremely variable (Ni/Cu between 0.1 and 71.5), while Ni and Pd tenors are consistent, indicative of the high mobility and variable concentrations of Cu sulfide within the deposit. Sulfur isotope signatures of the ore sulfides (δ34S ~6‰; Δ33S ~0‰) indicate a local crustal S contaminant from host marbles yet display S/Se ratios suggestive of a postmagmatic overprint. The consistent geochemical similarities of the bulk sulfide throughout the complex and the absence of primary silicate-sulfide textures suggest that the Munali ores were not sourced from a parental magma directly represented by units within the complex. Instead, it is suggested that the sulfide liquid was introduced from elsewhere in the magmatic system during the later stages of the emplacement of the complex. Fractional crystallization of the sulfide liquid during emplacement resulted in the primary segregation of a Cu-rich residual liquid that migrated away from the bulk of the Fe-Ni sulfide, accounting for the high bulk Ni/Cu ratio, with the potential for the accumulation of a separate and thus far undiscovered Cu orebody. In addition, intense deformation during the Pan-African orogeny and interaction with hydrothermal fluids have locally overprinted some of the primary magmatic textures, resulting in localized sulfide mobilization and the extreme variations of Ni/Cu ratio between sulfide samples. Munali therefore represents a complex dynamic deposit showcasing a variety of mechanisms for sulfide fractionation of an Ni-Cu-PGE orebody by both syn- and postmagmatic processes.