The separation of cobalt from zinc sulfate solutions by oxidation-precipitation process using peroxy-monosulfuric acid as oxidant has been presented according to the technological conditions of removal of cobalt from zinc electrolyte. After investigating the important parameters governing the separation of cobalt and their effect on the separation process, the optimal parameters of oxidation precipitation of cobalt were determined, the oxidation precipitation percent of cobalt was up to 90% under the conditions. The XRD analysis results of precipitates demonstrated that the precipitate was cobalt hydroxide oxide (CoOOH) in pure cobalt system while the precipitates were cobaltosic oxide (Co3O4) and basic zinc sulfate (ZnSO4(OH)6.H2O) in zinc-cobalt system.