In this paper, the galvanic effect of pyrite and arsenopyrite during the leaching pretreatment of gold ores was determined with the use of electrochemical testing (open circuit potential, linear sweep voltammetry, Tafel, and electrochemical impedance spectroscopy (EIS)) and frontier orbit calculations. The results show that (i) the linear sweep voltammetry curve and Tafel curve of the galvanic pair are similar to those of arsenopyrite, (ii) the corrosion behavior of the galvanic pair is consistent with that of arsenopyrite, and (iii) the galvanic effect promotes the corrosion of arsenopyrite by simultaneously increasing the cathode and anode currents and reducing oxidation resistance. The frontier orbit calculation explains the principle of the galvanic effect of pyrite and arsenopyrite from the view of quantum mechanics.