Novel catalytic carbon membranes (CCMs) were fabricated by a mixture of phenolic resin and nanosized copper-based catalyst as precursor, through the processes of blending, compressing, molding, and pyrolysis. The thermal stability of precursors was studied by thermogravimetric analysis. The surface morphology, carbon structure, pore structure, and catalytic reduction property of CCMs were characterized. The CCMs were applied to assembly reactors for the reaction of hydrogen production from methanol steam reforming. Comparative study of catalytic performance was made among the reactors of CCMs, traditional fixed bed, and inert carbon membranes. The methanol steam reforming in CCMs was investigated by some crucial operation variables, including reaction time, reactor configuration, streaming mode, space velocity, and molar ratio. Results have shown that the as-synthesized catalyst and CCMs are stable enough to tolerate the present reaction condition for a long life expectancy. Although the carbon matrix is favorable for dispersing and improving the effective exposure of copper-based catalyst to reactant, the distinct pore diffusion in CCMs is notable. The performance reaches 95% for methanol conversion and 92% for hydrogen yield when a CCM-assembled reactor is operated under the condition of two outlet streams, space velocity at 9.6 h(-1), and methanol/steam molar ratio of 1:1.