Based on the bioleaching mechanism and electrochemical studies of covellite, the dissolution rate of covellite mineral is accelerated through increasing the redox potential (Eh) of the leach. In the present work, some methods were adopted to enhance the bioleaching of covellite concentrate (collected from Zijinshan copper mine, Fujian province, China) by adding different oxidants such as pure pyrite, ferric ions and H2O2. The goal of this study was to provide appropriate operating parameters for the industry application and increase the efficiency of the bioleaching of copper mine. The results showed that the optimal way to increase the redox potential (Eh) level was the addition of pure pyrite. This method could effectively raise the Eh of bioleaching process while the effect of environmental change was negligible. It could quicken the leaching process and enhance the final copper recovery through the addition of pyrite by 1:1 or 1:2 ratio of covellite concentrate to pyrite.