The potentiometric determination of uranium is widely carried out in phosphoric acid medium to suppress the interferences of plutonium by complexation. Owing to the complexity of the recycling plutonium from the phosphate based waste involving manifold stages of separation, a method has been proposed in the present paper which does not use phosphoric acid. Uranium and plutonium are reduced to U/IV/ and Pu/III/ in 1M H2SO4 by Ti/III/, and NaNO2 is chosen to selectively oxidize Pu/III/ and the excess of Ti/III/. The unreacted NaNO2 is destroyed by sulphamic acid and excess Fe/III/ is added following dilution. The equivalent amount of Fe/II/ thus liberated is titrated against standard K2Cr2O7. R.S.D. obtained for the determination of uranium /1–2 mg/ is 0.3% with plutonium being present upto 4.0 mg.