A polymer inclusion membrane (PIM) composed of 50 wt% poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as its base polymer, 40 wt% Aliquat® 336 as its extractant and 10 wt% dibutyl phthalate (DBP) as plasticizer provided efficient extraction of vanadium(V) from its sulfate solutions adjusted to pH 2.5. It was suggested that V(V) was extracted as VO2SO4− via an anion exchange mechanism. Quantitative back-extraction was achieved in a sulfuric acid solution (6 mol L-1) containing 1 v/v% of hydrogen peroxide. It was assumed that the back-extraction process involved the oxidation of VO2+ to VO(O2)+ by hydrogen peroxide. The newly developed PIM with the optimized composition mentioned above exhibited excellent selectivity for V(V) in the presence of metallic species present in digests of spent alumina hydrodesulfurization catalysts (i.e., Al(III), Co(II), Cu(II), Fe(III), Mn(II), and Ni(II)). The co-extraction of Mo(VI) with V(V) was eliminated by its selective extraction at pH 1.1. The optimized PIM was characterized by contact angle measurements, atomic-force microscopy (AFM), energy dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA)/derivatives thermogravimetric analysis (DTGA), and the stress-strain measurements.