To achieve end user’s specified PuO₂, controlling and monitoring of Pu in its fourth valency state is essential prior to the conversion of Pu-nitrate to its oxide through oxalate precipitation process. Conventional radiometric procedure for the analysis of Pu oxidation state in Pu-nitrate solution containing trace level of Pu(III) has limitation due to oxidation of Pu(III) during the sample preparation with respect to acidity. A simple direct spectrophotometry using an optic fiber  spectrophotometer was attempted for the estimation of trace level of Pu(III), after separating the bulk amount of Pu(IV) by maintaining the sample acidity. By using a synergistic mixture of 30 % TBP and 1 M theonyl trifluoro acetone in benzene, the Pu(IV) could be removed to a level which doesn’t interfere in the Pu(III) absorption.