Comparative solvent extraction studies of Zr and Hf were carried out from acidic chloride and potassium fluoride solutions with 1 or 2-octanol as extractants. The extraction process was experimentally investigated as a function of contact time, hydrochloric acid concentration, sulfuric acid concentration, hydrofluoric acid concentration, nitric acid concentration, amount of potassium fluoride added and organic-to-aqueous phase ratio. The results show that zirconium is preferentially extracted into the organic phase. Under the optimal operating conditions of 10 % HCl, 1.5 M KF, 15 minutes and an organic-to-aqueous phase ratio of 2:1, the extraction percentage of zirconium and hafnium is 94.3 % of Zr and 64.3 % of Hf and a separation factor of 9.2 for 2-octanol and 93.1 of Zr and 60.9 % of Hf and a separation factor of 8.7 %. 2-octanol shows a slightly higher extraction percentage and separation factor over 1-octonal.