Surface oxidation is one of the most important factors that influence the flotation selectivity and recovery in the processing of complex sulphide ores. It is an inherent part of surface chemical reactions that determine whether the surface film formed on a sulphide mineral will act as a hydrophobic or hydrophilic one. Because of the highly complex surface chemistry and mineralogy involved the results of flotation tests may often be difficult to interpret. In this paper, the flotation behaviour of nickel-copper ores processed in the Sudbury area is discussed with emphasis on the effect of oxidation on individual minerals, primarily pyrrhotite. In general, moderate oxidation of a freshly ground ore promotes the flotability of all principal sulphides in the ore leading to a bulk flotation concentrate. The ease of individual mineral flotability under normal aeration conditions, which is chalcopyrite > pentlandite > pyrrotite, changes to pentlandite > chalcopyrite > pyrrhotite under oxygen-deficient conditions. This behaviour is correlated with the catalytic activity of these minerals for oxygen reduction. On the other hand, preferential oxidation of pyrrhotite may lead to a selectivity increase in flotation. Such a behaviour has been noted in the flotation of a pyrrhotite-rich process stream. The results have been discussed in the light of fundamental electrochemical interactions involving pentlandite, chalcopyrite, pyrrhotite, pyrite and grinding media and a mechanism has been proposed to explain the selectivity.