Microstructured catalysts have recently occupied the attention as promising catalytic materials due to their efficient diffusion property of heat and reactants during various catalytic reactions. In this study, we successfully prepared the novel microstructured catalyst composed of copper-zinc oxide (Cu/ZnO) catalyst powder and ceramic fiber by using a high-speed and low-cost papermaking technique. As-prepared materials, called paper-structured catalyst in this study, were cardboard-like, lightweight, flexible and easy-to-handle in practical use. The fine Cu/ZnO catalyst powders were well scattered on the layered ceramic fiber-network microstructure (average pore size: ca. 20 µm, porosity: ca. 50%) in the paper composite. Subsequently, paper-structured catalysts were applied to the autothermal reforming of methanol to produce hydrogen for fuel cell applications. The methanol conversion performed with the paper-structured catalyst reached up to ca. 90% comparable with that of the original catalyst powder, surpassing by far that of the commercial pellet-type catalyst. In general, the carbon monoxide by-product acts as a catalytic poison for the Pt anode electrocatalyst of fuel cells. In the case of the paper-structured catalyst, the carbon monoxide concentration was drastically reduced to around 3000 ppm, which was less than half that produced with catalyst powder. Besides, paper-structured catalyst showed a high catalytic durability; the decrease in the methanol conversion was only ca. 6% during long-term cycle reforming test, whereas the performance of original catalyst powder decreased by ca. 20%. The flow rate of the generated gas and the internal temperature of the reactor with paper-structured catalyst were relatively stable as compared with powder and pellet; therefore it was suggested that the paper-specific fiber-network microstructure possibly provided a uniform flow of heat and reactants inside the catalyst layer, and contributed to some improvement of catalytic stability as well as reactivity and durability. The paper-structured catalysts having paper-like flexibility and fabricating properties are allowed to fit various reactor configurations, and thus are expected as promising materials for improving the practical utility and catalytic performance in the catalytic gas-reforming process.