In this work, the interactions between one sample of silver-bearing tailing (223 g/t silver) and chalcopyrite during bioleaching by mixed moderately thermophilic culture were investigated. Bioleaching results showed that copper can be almost totally extracted from chalcopyrite as the result of addition of the silver-bearing tailing, and silver (Ag) extraction can be significantly improved with the addition of chalcopyrite. Hence, cooperative bioleaching process of chalcopyrite and the chosen silver-bearing tailing was feasible. Ag mainly occurred as silver sulfate (Ag2SO4), and further work of enhancing the Ag extraction and its recovery is currently in progress. The catalytic effect of the silver-bearing tailing on chalcopyrite dissolution was investigated mainly with X-ray photoelectron spectroscopy (XPS) and electrochemical analysis. Results proved that the presence of the silver-bearing tailing enhanced the oxidation rate of chalcopyrite and also eliminated the passivation effect of polysulfide, thus resulting in an extremely high copper extraction. (C) 2015 Elsevier Ltd. All rights reserved.