The reaction mechanism for the cathodic decomposition of pyrrhotite in deoxygenated solutions at natural, near neutral pH levels was studied using potential and cyclic voltammetric measurements. Reaction products on the pyrrhotite surfaces were examined by Auger Electron Spectroscopy (AES), by X-ray photoelectron spectroscopy (XPS) and by analyzing the voltammograms for the electron balance of the reactions. Surface properties of the pyrrhotite/solution interface were characterized using an ac impedance technique. The parameters of an equivalent circuit were determined by the nonlinear least-squares fit (NLLSF) technique. The effect of cathodic polarization on floatability was investigated by performing microflotation tests. Possible implications to the flotation separation of chalcopyrite-pyrrhotite ores are discussed.