Using sodium diethyldithiocarbamate as a collector the flotation behavior of pyrrhotite was investigated. The relationship between potential and pH range for pyrrhotite flotation was established. The results show that the flotation of pyrrhotite is dependent on pulp potential at certain pH values. Pyrrhotite has good floatability from pH 2 to pH 12, and poor flotability at pH>12. Cyclic voltammetry and Fourier transform infrared spectrum analysis show that the major adsorption product of DDTC on pyrrhotite is tetraethylthiuram disulfide. The intensity of Fourier transform infrared signals of tetraethylthiuram disulfide adsorbed on pyrrhotite and the anode current of a pyrrhotite electrode and flotation response of pyrrhotite are correlated with pulp potentials.