A novel combined organic and inorganic process for preparing thin supported membrane was developed, using which a thin and defect-free Pd membrane with uniform thickness of 5 microm was directly coated onto porous alpha-Al2O3 hollow fiber without any interlayer and substrate penetration; at the same time, there existed a small interstice between membrane and substrate, which led to higher hydrogen permeance, infinite selectivity, and better membrane stability.