Properties of surface films on chalcopyrite and pyrite differ due to variations in the mechanism of oxidation of the two minerals. In the case of chalcopyrite the first step in the oxidation is the release of iron as ferric ions, which hydrolyse depending upon conditions prevalent in solution. The iron oxide/hydroxide layer formed by hydrolysis of ferric ions is quite porous and easily detachable from the surface of chalcopyrite. When the surface oxide layer is detached a sulphur-rich layer is exposed making chalcopyrite hydrophobic. The thickness and properties of the sulphur-rich layer determine its flotation response, both in the absence and presence of collectors. In the case of pyrite, on the other hand, iron is released as ferrous ions which require much higher pHs to hydrolyse. These ions remain adsorbed on the surface of pyrite making the surface hydrophilic. When the iron species are complexed with chelating agents such as ethylene diamine tetra acetic acid, pyrite was hydrophobic. Siderite forms in the presence of carbonate ions, which might be present in several flotation systems. Siderite nucleated on isolated sites at the surface. The presence of such a precipitate is likely to influence the interaction of pyrite with various reagents thereby altering its flotation behavior. To determine the mechanism of oxidation, kinetics of oxidation of chalcopyrite and pyrite was studied using several electrochemical techniques, namely, cyclic voltammetry, polarisation and impedance spectroscopy. Floatability of the minerals was investigated by measurement of contact angles on mineral electrodes and by Halimond tube flotation. Impedance spectroscopy was especially useful for estimating various properties of surface film for both the minerals. Properties such as charge transfer resistance, porosity, and capacitances of the surface films on the two minerals are compared under several conditions of oxidation. These properties were found to be a strong function of the rate and the extent of oxidation.