Liquid-liquid extraction of Th(IV) and U(VI) has been investigated by commercial extractant PC-88A in toluene. The optimum conditions for extraction of these metals have been established by studying the various parameters like acid concentration/pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.1–1.0M HNO3 acid and in the pH range 1.0–4.0 while U(VI) was completely extracted in the pH range 1.0–3.5 with 2.5·10–2M and 2.·10–2M PC-88A in toluene, respectively. The probable extracted species have been ascertained by log D-log C plot as ThR4·4HR and UO2R2·2HR, respectively. The method permits separation of Th(IV) and U(VI) from associated metals with a recovery of 99.0%.