The studies of pulp electrochemical flotation separation of pyrite and arsenopyrite were made from the thermodynamics, mineral natural oxidation rate, property of mineral surface oxidised material and pulp electrochemical flotation tests. The results showed that although pyrite and arsenopyrite possessed similar thermodynamic stability, significant differences of two minerals were observed in natural oxidation rate, property of surface oxidised material and its influence to dixanthogen formation on the oxidised mineral surface. Based on the non-thermodynamic differences, the pulp electrochemical flotation technology was successfully used to separate arsenopyrite from pyrite in pilot test.