Abstract: The electrolytic oxidation of Ce (Ⅲ) was investigated in detail with platinized titanium anode in HNO3 medium. The effects of the concentration of HNO3 and Ce (Ⅳ), the mixing time of organic and aqueous phases etc. on the extraction distribution coefficient of Ce (Ⅳ) by 0.3M HDEHP-0.2M TBP/kerosene-240, as well as the electrolytic oxidation of Ce (Ⅲ) in the presence of the extractant were studied. A procedure was developed for the separation of Ce from Pm through Ce (Ⅲ)-electrolytic oxidation, Ce (Ⅳ)-extraction and Ce (Ⅳ)-reduction strip, and the recovery for Ce and Pm was found to be 95.5% and 98.5% respectively. It is interesting to note that the distribution coefficient of Ce(Ⅳ) decreases with increasing intensity of light probably due to photoreduction of Ce (Ⅳ) by organic solvent.