With a view to mitigate the complexities associated with aqueous solubility of Organophosphorous solvent, accurate estimation of dissolved organic in aqueous streams assumes great importance. Present method employs solvent extraction using 10 % (v/v) mixture of benzyl alcohol-benzene (BBA) for selective enrichment/extraction of dissolved Dibutyl phosphosphoric acid (HDBP), the target analyte, in presence of tributyl phosphate from nitric acid solutions containing bulk amount of uranyl ions. The extracted HDBP after methylation is subjected to gas chromatographic analysis using thermal conductivity detector. A calibration plot of HDBP estimation in the concentration range of 10–100 ppm, yields a precision with RSD of ±5 %.