The surface sulfur speciation of chalcopyrite leached by moderately thermophilic Sulfobacillus thermosulfidooxidans was investigated by employing scanning electron microscopy (SEIM), X-ray diffraction (XRD) and sulfur K-edge X-ray absorption near edge structure spectroscopy (XANES), accompanying with the leaching behavior elucidation. Leaching experiment showed that there was an optimum range of the redox potential for chalcopyrite dissolution. Leaching products were found accumulating during the leaching process, which might be jarosite according to the XRD analysis. The sulfur K-edge spectra indicated that chalcocite might be the intermediate sulfur compound under a critical redox potential, which might explain the existence of optimum range of the redox potential and provide an evidence for the two-step leaching model of chalcopyrite at low Eh. In addition, the results of sulfur K-edge spectra showed jarosite would accumulate on mineral surface, which might be the main component of the passivation layer. (C) 2009 Elsevier B.V. All rights reserved.