To prepare H-2-permeable palladium composite membranes, a novel carbon-doped microporous TiO2 intermediate layer was introduced to modify the surface of macroporous Al2O3 substrates. The Pd/TiO2-C/Al2O3 membrane was prepared via electroless plating, and thereafter, carbon residue in the intermediate layer was removed by calcination in air, yielding a Pd/TiO2/Al2O3 membrane. Experimental results indicate that the carbon residue shrinks the pore size of the intermediate layer and facilitates a decrease of membrane defects. Additionally, carbon removal induces a higher effective membrane area at the permeate side, which enhances hydrogen permeability. Furthermore, the apparent activation energy (E-A) and stability of the as-prepared Pd/TiO2/Al2O3 membrane were investigated.