Complex sulfide ores are usually found as a mixture of various sulfide and gangue minerals, and froth flotation is the predominant method for the selective separation of sulfide minerals. Adherence and contact between sulfide minerals are inevitable during froth flotation, and galvanic interactions between sulfide minerals will occur because of differences in rest potentials. However, the effect of these galvanic interactions on the selective flotation of sulfide minerals have been rarely studied. In this work, the effect of the galvanic interaction between pyrite and sphalerite on the flotation behavior and surface characteristics of pyrite was investigated by micro-flotation tests, collector adsorption tests, electrochemical techniques and XPS (X-ray photoelectron spectroscopy) surface analysis. The micro-flotation tests indicated that the floatability of pyrite decreased in the pH range of 4.0 to 9.5 and increased under strongly alkaline pH conditions (pH > 10) due to the galvanic interaction. The collector adsorption results demonstrated that the adsorption capacity of the collector on the pyrite surface was significantly reduced because of the galvanic interaction between pyrite and sphalerite. The electrochemical measurements revealed that the decrease in the oxidation current of xanthates to dixanthogen was responsible for the decreasing adsorption capacity of the collector on the pyrite surface. The XPS results indicated that the formation of the S_2 O_3^(2-) oxidation product on the pyrite surface decreased at a strongly alkaline pH due to the galvanic interaction. Therefore, pyrite floatability improved at an alkaline pH. These results consistently showed that the galvanic interaction between pyrite and sphalerite had an important influence on the floatability and surface characteristics of pyrite.