The effect of extracelluar polymeric substances(EPS) on the bioleaching chalcopyrite concentrates in the presence of iron- and sulphur-oxidizing bacteria (A.ferrooxidans) was studied.The bacterial number,pH,redox potential,and the concentrations of Fe2+and Cu2+ ions were investigated.The leached residues were analyzed by the X-ray diffraction and FT-IR.The results indicate that the EPS makes the bacteria adhere to the chalcopyrite surface easily and it is helpful for bacteria in disadvantageous environment.At the same time,EPS film layer with Fe3+ deposits on the surface of chalcopyrite and becomes a barrier of oxygen transfer to chalcopyrite to passivate chalcopyrite,and creates the high redox potential space through concentrating Fe3+ ions to accelerate bioleaching pyrite in chalcopyrite concentrates.The results suggest that EPS formation promotes bioleaching pyrite and inhibits bioleaching chalcopyrite,especially under high potential condition.