The effects of metal ion addition rates and contact time on the activation of synthetic sphalerite using copper, cadmium and silver ions were determined in order to investigate the exchange characteristics at the mineral surface. The stoichiometry of the adsorption indicated that the activation of sphalerite involved both a simple ion exchange and redox process in which the activating ion and oxygen were reduced, and the mixed-sulphide surface was oxidised to produce elemental sulphur and a metal-deficient sulphide surface. Unactivated sphalerite was shown to be relatively hydrophilic, with recoveries usually less than 20 per cent for a five-minute float. Activated sphalerite could be readily floated without the use of a conventional collector. This inherent flotability of the activated sphalerite had previously been associated with the formation of a metal-deficient sulphide layer; however, this study emphasizses the significance of the surface oxidation processes occurring.