Chromite tailings assaying 21.2 per cent Cr2O3 was upgraded to 48.7 per cent Cr2O3 at a recovery of 72.0 per cent using column flotation with a mixture of anionic collectors at pH 11. Electrokinetic methods were used to elucidate the mechanism of collector adsorption and correlate the findings with the optimum flotation conditions. Multivalent constituent ions such as Cr3+, A13+, Fe2+ and Mg2+ were found to adsorb on chromite surface and shift the zpc of chromite in the direction of oxide form of the mineral. The anionic collectors also imparted a negative charge to chromite in the entire pH region. The higher zeta potentials obtained upon adding the anionic collectors is ascribed to the adsorption of anionic surfactant onto the positively charged chromite surface. The positive sites are generated through formation of significant amount of hydroxy complexes of magnesium at pH 11. Complementary infrared data reveal the absence of a shift in the spectra indicating the possibility of physical adsorption in the system.