The surface analytical techniques of X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) have provided information on the type and concentration of species on the surface of sphalerite and pyrite particles in flotation concentrate and tail samples, but also on their distribution on each particle and across particles of different sizes. From this surface analytical study, a more accurate interpretation of the flotation results of sphalerite and pyrite minerals in a mixed mineral system could be made as a function of the concentrations of copper sulphate activator and xanthate collector, and particle size. In particular, it was found that sphalerite particles reporting to the concentrate are larger in size and contain less iron hydroxide on their surface than particles reporting to the tail. As for the pyrite particles, their lower recovery than the sphalerite particles is the result of a larger proportion of iron hydroxide on their surface inhibiting copper and collector adsorption. (C) 2003 Elsevier Science B.V. All rights reserved.