The function of microorganism and dissolution reaction pathway of carrollite in the bioleaching process were investigated. The results showed that both indirect and contact mechanisms influenced the leaching process. The dissolution of carrollite was significantly accelerated when bacteria were adsorbed on the mineral surface, indicating that the contact mechanism significantly affected the dissolution of carrollite. During bioleaching, the sequence of oxidation state of the sulfur moiety of carrollite was as follows: S?2→S0→S+4→S+6. Elemental sulfur precipitated on the mineral surface, indicating that the dissolution of carrollite occurred via the polysulfide pathway. The surface of carrollite was selectively corroded by bacteria, and oxidation pits with different sizes were observed at various sites. Elemental sulfur, sulfate and sulfite were present on the surface of carrollite during the leaching process, and may have formed a passivation layer on mineral surface.