The effects of silver sulfide (Ag2S) on the bioleaching of chalcopyrite and pyrite were investigated in this paper. It has been shown that Ag2S enhanced the yields of bioleaching of chalcopyrite but inhibited the bio-oxidation of pyrite. The addition of Ag2S selectively increased the copper dissolution from the chalcopyrite-containing ores in shake flasks with a recovery of 85.3% compared with 24.3% without Ag2S, while slightly decreased the iron yields from 51% to 41.8%. The copper extraction of the chalcoopyrite-containing waste rock in column leaching charged with 18 kg mass increased up to 21.7% in the presence of Ag2S, while only 3.4% in the absence of the catalyst. The mechanism of Ag2S catalysis could be explained well by the "Mixed potential model".