Electrolytic flotation, a rather unconventional flotation technique used in effluent treatment, was investigated on pyrite; the process was enhanced by xanthate and also a cationic collector. This was then compared with classical floatability experiments. Zeta-potential measurements, under similar pulp conditions, were carried out to explain the process mechanism. The mineral flotation behavior in the presence of common modifiers was also examined during electrolytic flotation. The latter produces fine gas bubbles, has favorable hydrodynamic conditions and assists in flocculation of particles prior to flotation, as shown.