With the view point of recovery of pure solvent components from degraded PUREX (Plutonium URanium Extraction) solvent, comprising of mixture of 30% TBP-HDBP-n-dodecane, three homologues of room temperature ionic liquids (C(n)mimCl, n = 4, 6, 8) have been investigated in batch equilibration mode (liquid-liquid extraction). While lower homologues of RTIL (C-4 and C-6) could effectively separate out HDBP from pure TBP-HDBP-n-dodecane mixture, the higher homologue C(8)mimCl could quantitatively remove TBP and HDBP together leaving behind pure n-dodecane as organic phase. Efficacy of RTIL solutions have also been studied as a function of RTIL concentration, composition of various components in organic mixture, kinetics of extraction, etc. These ionic liquids were found to retain their efficacy even after five cycles of operation after their regeneration. Studies from actual degraded solvent showed that C(8)mimCl could remove HDBP quantitatively and TBP (similar to 45% of the initial concentration) whereas C(6)mimCl and C(4)mimCl showed very little extraction even for HDBP. The mechanism of extraction was found to be formation of micelles and ion-pair formation. (C) 2013 Elsevier B.V. All rights reserved.