The composition of passive layer of chalcopyrite was investigated by X-ray photoelectron spectroscopy(XPS), accompanied with cyclic voltammetry(CV). The leaching experiment shows that the extraction rates of Cu with leaching for 30 d by sterile control and microorganisms are 4.0% and 21.5%, respectively. In comparison, 3.8% and 10.5% Fe are leached by sterile control and microorganisms, respectively. The results of XPS studies suggest that Fe atoms dissolve preferentially from the chalcopyrite lattice, and disulfide(S22-), polysulfide(Sn2-) and elemental sulfur(S0) are identified on the chalcopyrite surfaces leached by sterile control and microorganisms. Additionally, sulfate(SO42-) is detected on the chalcopyrite surfaces leached by microorganisms, and most of it probably originates from jarosite. The analysis of CV results reveals that metal-deficient sulfide(Cu1-xFe1-yS2-z, yx) and elemental sulfur(S0) passivate the surface of chalcopyrite electrode. The elemental sulfur and/or jarosite coating on the chalcopyrite surface may have impact on the leaching process; however, the disulfide, polysulfide or metal-deficient sulfide plays a more key role in the chalcopyrite leaching.