Chalcocite is one of the most industrially valuable copper-bearing minerals available for bioleaching. However, the efficiency of chalcocite bioleaching remains unsatisfactory. To better understand the bioleaching process of chalcocite, researches on chemical-biological dissolution mechanisms and leaching kinetics are reviewed. The crystal structure of chalcocite is systematically characterized. The mechanisms for chemical dissolution, electrochemical dissolution, and biological dissolution are summarized and elaborated. The effects of leaching parameters on the leaching kinetics are discussed, and issues in industrial-scale bioleaching are identified. However, the fine leaching process and leaching mechanism of chalcocite still require further study. New research techniques, including synchrotron radiation-based measurements, can be employed to determine the fine mechanism for chalcocite dissolution with interdisciplinary chemistry-biology studies, which may enable efficient extraction of copper from chalcocite in the future.