A supported liquid membrane system using hollow fiber membranes as supports (HFSLM) has been studied for the separation of zirconium and hafnium, which are typical metal pairs with extreme similarity in chemistry. Tri-n-octylamine (TNOA) and trioctylmethyl ammonium chloride (Aliquat 336) were used as carriers. The effect on the transport and separation of Zr and Hf of HCl concentrations in the feed and stripping solutions, hollow fiber length, flow rate of aqueous phases was investigated. The mechanism of transport through the HFSLM is discussed. The controlling step for the liquid membrane process was the diffusion in the membrane, except at low flow rates. The HFSLM acquires a maximum Zr/Hf flux ratio of about 160, which is 20 times than that of a flat-sheet system reported previously.