With the extensive exploitation and gradual depletion of high-grade copper reserves, the mining industry is paying more and more attention to the hydrometallurgical extraction of copper from low_x0002_grade and arsenic bearing copper ores. Hydrometallurgical processing, such as heap leaching, column leaching and bioleaching, provide a viable alternative to the traditional pyrometallurgy due to its harmony with the environment, moderate capital investment, and low operating costs. However, the slow leaching kinetics of enargite (Cu3AsS4) and chalcopyrite (CuFeS2) remain problematic for commercial leaching practice. The formation mechanism and the nature of the passivating layers during leaching is still a matter of debate in hydrometallurgical research. In this study, the dissolution mechanism of enargite and chalcopyrite in sulfuric acid solution was investigated using a range of electrochemical and spectroscopic analysis methods. Electrochemical oxidation of enargite demonstrated an obvious passivation region from 500 to 750 mV (Ag/AgCl). The formed passivation film was found a n-type semiconductor behaviour, which is different from the original enargite with a p-type behaviour. The results of X-ray photoelectron spectroscopy (XPS) suggested that a nonstoichiometric film Cu(3−x)As(1−y)S4 (x>>y) accumulated on the electrode surface, which accounted for the obvious decrease in current density in the passive potential region. For chalcopyrite, three important potentials of 550, 680 and 730 mV which are related to the formation and dissolution of passivation film were observed based on the cyclic voltammetry (CV) and potentiodynamic polarisation. Raman and X-ray absorption near edge structure (XANES) spectra studies of the chalcopyrite electrodes after being treated under these three potentials indicated a metal-deficient sulfide of Cu1−xFe1−yS2 (y>>x) might be responsible for the passivation phenomenon. Hence, it is concluded that the passivation of enargite and chalcopyrite are similar which are caused by metal_x0002_deficient sulfide surfaces although the compositions of the metal-deficient sulfide are different.