In this research, porous inorganic membranes for hydrogen separation were prepared with α-alumina support by multi-step pore modification method. Porous inorganic membranes were made by three consecutive steps : sol-gel method in-situ hydrolysis of tetraethylorthosilicate (TEOS) and soaking and vapor deposition (SVD) method. In order to enhance the hydrogen selectivity, we used nickel (Ni) and palladium (Pd) particles in the first and final pore modification steps. Although both nickel and palladium induced surface diffusion, palladium was shown more effective for hydrogen selective adsorption than nickel. This multi-step method produced porous membranes with a moderate hydrogen selectivity and excellent hydrogen permeability at high temperature up to 773 K and at transmembrane pressure (△P) as high as 310 kPa. The separation factor of hydrogen relative to nitrogen was maintained at about 7 even when the transmembrane pressure was 70 kPa, and the hydrogen permeability was still much higher than that of non-porous polymeric membranes. Furthermore, the distributions of nickel and palladium within the intermediate layer formed at the membrane cross-section were examined by scanning electron microscopy (SEM) and energy dispersive X-ray analysis.