Further to the previous study on the extractive recovery of V(V) from HCl solution by some alkanols, the extraction of V(V) from HCl solutions by 1-pentanol and 3-methyl -1-butanol (isomers) dissolved in n-heptane were investigated in the present study, still propelled by the need to proffering viable alternatives to the scarce and relatively costly organophosphorous extractants, and also compare the extraction efficiency of straight-and branched-chain extractants. At the studied pH range (0.5-4.0) with 1-penttanol as extractant, the percentage V(V) extraction (extraction efficiency, E%) reached optimum E%= 40.0 at pH of 3.0 and for 3-methyl-1-butanol, optimum E% was 36. respectively, indicating exothermic/endothermic extraction processes. The isomer 3-methyl -1-butanol gave a higher extraction efficiency after a three-stage extraction (E% = 92.5) than 1-pentanol (E% = 83.4). Recycling experiment revealed both to be recyclable. From slope analysis, analytical and spectra data, the extracted complexes have been formulated as VO 2 Cl.nROH and (VO 2 Cl) m .nROH (where m>> n) at low and high concentrations of extractant, respectively. On the whole, 3-methyl-1-butanol was assessed as fairly better as an extractant for vanadium (V) at lower temperature experimental conditions. The effect of methyl branched-chain played an insignificant role on the extraction.