Sixteen metal sulphides with widely differing solid state, chemical and electrochemical properties have been investigated with respect to their suitabilityasanenergy source for Thiobucillus ferrooxiduns. The most critical rate-determining parameter for bacterial oxidation (in the absence of any electron acceptors, e.g. Fe3+) was the solubility product of the sulphide. Deviations from the systematic dependence are, however, observed when a large concentration of the holes are present in the semiconducting sulphide (p-type conduction), or when holes are generated through electron extraction from the sulphide surface (e.g. by Fe3+). The experimental results are consistent with a mechanism in which Th. ferrooxiduns utilises H+ and Fe3+ as catalytic agents which break surface bonds by chemical and electrochemical mechanisms, respectively. They are subsequently recycled while the bacterium oxidises the generated surface products, -SHS-and SO, etc., to sulphate. On the basis of the derived mechanism it should be possible to estimate and predict the suitability of sulphides for bacterial oxidation and to analyse the influence of crystalline quality and impurities, as well as the composition of the solution, on the rate of oxidation.