Approximately 20% of current world copper cathode output is produced using a hydrometallurgical process route, generally referred to as the leach-solvent extraction-electrowinning flowsheet. Since its commercialization in the late 1960s, steady improvements in the performance and efficiency of the solvent-extraction reagents and equipment, combined with significant developments in leaching and electrowinning, have made an ever-widening range of ore types amenable to this technology. Following successful implementation on all major continents, a large proportion of growth in recent years derives from the re-emergence of copper solvent extraction in the Central African Copperbelt. This review provides a brief history of the development and evolution of copper solvent extractants and mixer-settler contactors, and the significance of the Copperbelt region in achieving commercialization and acceptance of the technology. The opportunities and challenges presented by the abundant high-grade oxide ores of the Copperbelt are contrasted with the processing of solutions derived from the low-grade mixed oxide-sulfide ore bodies that are prevalent in other geological regions. The current status of hydrometallurgical copper production in the African Copperbelt, within a global context, and a medium-term outlook for the technology are discussed.