The Central African Copperbelt (CACB) is Earth’s largest repository of sediment-hosted copper and cobalt. The criticality of these elements in battery technology and electricity transmission establishes them as fundamental components of the carbon-free energy revolution, yet the nature and origin of the hydrothermal fluids responsible for ore formation in the CACB remain controversial. Here, we present microthermometric, scanning electron microscopy and laser ablation–inductively coupled plasma–mass spectrometry analyses of fluid inclusions from the Nkana-Mindola deposits in Zambia. We find that base metal concentrations vary by one to two orders of magnitude between “barren” and “ore” fluids, with concomitant distinctions in major salt chemistry. Primary fluid inclusions, hosted by pre- to synkinematic mineralized quartz veins, are characterized by high homogenization temperatures (~200–300 °C) and salinities, with K/Na >0.8 and elevated metal concentrations (102 to 103 ppm Cu and Co). Conversely, barren, post-kinematic vein quartz contains lower homogenization temperature (~110–210 °C) and lower-salinity primary inclusions, characterized by K/Na <0.8 with low metal contents (<102 ppm Cu and Co). We propose a model in which high-temperature, sulfate-deficient, metalliferous, potassic residual brines, formed during advanced evaporation of CaCl2-rich, mid-Neoproterozoic seawater, were responsible for ore formation. During basin closure, lower-temperature, halite-undersaturated fluids interacted with evaporites and formed structurally controlled, sodic metasomatism. Reconciliation of these fluid chemistries and base metal concentrations with reported alteration assemblages from a majority of Zambian Copperbelt deposits suggests highly evolved, residual brines were critical to the formation of this unique metallogenic province.