The abilities of acidophilic chemolithotrophic bacteria and archaea to accelerate the oxidative dissolution of sulfide minerals have been harnessed in the development and application of a biotechnology for extracting metals from sulfidic ores and concentrates. Biomining is currently used primarily to leach copper sulfides and as an oxidative pretreatment for refractory gold ores, though it is also used to recover other base metals, such as cobalt, nickel and zinc. Recent developments have included using acidophiles to process electronic wastes, to extract metals from oxidized ores, and to selectively recover metals from process waters and waste streams. This review describes the microorganisms and mechanisms involved in commercial biomining operations, how the technology has developed over the past 50 years, and discusses the challenges and opportunities for mineral biotechnologies in the 21st century.