The bioleaching of djurleite was investigated using Acidithiobacillus ferrooxidans. XRD and XPS were used to analyzes the bioleaching mechanism of djurleite. The results have shown copper extraction for djurleite under optimal conditions was 95.12%. During the bioleaching, Djurleite was firstly converted to CuS, then to Cu2+ and S0. Display omitted ► Bioleaching of djurleite using Acidithiobacillus ferrooxidans was investigated. ► A few Cu(II) exists in the lattice of djurleite. ► Djurleite was firstly converted to CuS, then to Cu2+ and S0. The bioleaching of djurleite using Acidithiobacillus ferrooxidans (LD-1) was investigated in this paper. Experiments were carried out in shake flasks at pH 2.0, 160r/min and 30°C. The leaching residues were analyzed using X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The total copper extraction of djurleite under optimal condition reached 95.12%. The XRD analysis indicated the residues mainly consisted of ammoniojarosites and S8. It was observed by the SEM image that the djurleite was heavily etched. The XPS results confirmed the intermediate product formed during djurleite leaching was CuS. The result indicates the reaction pathway is: Cu31S16→CuS→tCu2+ and S0.