The development of compact hydrogen separator based on membrane technology is of key importance for hydrogen energy utilization, and the Pd-modified carbon membranes with enhanced hydrogen permeability were investigated in this work. The C/Al2O3 membranes were prepared by coating and carbonization of polyfurfuryl alcohol, then the palladium was introduced through impregnation-precipitation and colloid impregnation methods with a PdCl2/HCl solution and a Pd(OH)(2) colloid as the palladium resources, and the reduction was carried out with a N2H4 solution. The resulting Pd/C/Al2O3 membranes were characterized by means of SEM, EDX, XRD, XPS and TEM, and their permeation performances were tested with H-2, CO2, N-2 and CH4 at 25 degrees C. Compared with the colloid impregnation method, the impregnation-precipitation is more effective in deposition of palladium clusters inside of the carbon layer, and this kind of Pd/C/Al2O3 membranes exhibits excellent hydrogen permeability and permselectivity. Best hydrogen permeance, 1.9 x 10(-7) mol/m(2) s Pa, is observed at Pd/C = 0.1 wt/wt, and the corresponding H-2/N-2, H-2/CO2 and H-2/CH4 permselectivities are 275, 15 and 317, respectively. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.