Antimony pentafluoride (SbF5)/porous metal fluorides (PMF) were prepared by impregnating PMF with SbCl5, and then fluorinating with anhydrous hydrogen fluoride (AHF). It demonstrates excellent activity in vapor-phase catalytic fluorination and overcomes such drawbacks as hygroscopicity, corrosion and toxicity that appear while SbF5 was used alone. Furthermore, SbF5/PMF was characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement and SEM. Its catalytic activity was evaluated for vapor-phased fixed-bed catalytic fluorination. (c) 2005 Elsevier B.V. All rights reserved.