An environmentally benign method to separate iron and cobalt has been developed using a safe chemical, polyvinylpyrrolidone (PVP). The method involves dialysis of PVP–Fe and PVP–Co complexes against triple-distilled water. 59 Fe and 60 Co were used as radioactive tracers of iron and cobalt throughout the experiment. No other chemicals are required for clean separation of cobalt from iron. The optimum condition for separation has been obtained at pH 5 using 10% aqueous solution of PVP. The method is applicable from trace scale to macro-scale. Very high separation factors have been obtained.