Leached solution, generated by oxalic acidwashing of spent residue hydrodesulfurization (RHDS) catalyst, was used for separation and recovery of vanadium. First of all, solvent extraction, using mixture of 20% (v/v) Alamine-336 and 5% (v/v) tri-butyl phosphate (TBP) as a phase modifier, was conducted to extract molybdenumcompletelyat pH0.50. Then molybdenum-free solutionwas used for vanadium extraction at pH 1.25 with 20% Alamine-336 and 5% TBP. Stripping of vanadium from loaded organic solution was performed with 1.5MH2SO4 at O/A phase ratio of 5:1 where more than 99% of vanadiumwas stripped in two stages. The stripped vanadium solution was further processed by precipitating with ammonium hydroxide to recover ammonium-meta-vanadate which was calcined to obtain vanadium pentoxide. Finally a conceptual process was established for recovery of high purity vanadium pentoxide from oxalic acid leached solution of spent residue hydrodesulfurization (RHDS) catalyst.