The urea-nitrate combustion and homogeneous precipitation methods have been comparatively examined for the preparation of CuO/CeO2/ZrO2/Al2O3 catalysts. Their physicochemical properties, as well as their hydrogen production ability via the steam reforming of methanol, have been studied. Prepared catalysts were characterized using XRD, FESEM, EDX, BET, and FTIR analyses. Characterization analyses and catalytic performance studies showed that the preparation method plays an important role in the synthesis of catalysts. XRD analysis showed that the homogeneous precipitation method can prepare catalyst with smaller copper crystallites and better surface dispersion compared with the combustion synthesis method. EDX results illustrated homogenous dispersion of elements. BET and FESEM showed the surface area improvement and lower size distribution, respectively, during synthesis of catalysts by the homogeneous precipitation method. Catalytic performance study also proved that catalyst prepared by the homogeneous precipitation method had better methanol conversion at all temperatures, whereas the sample fabricated by the urea-nitrate combustion synthesis method produces less CO. The stability test showed that the catalyst synthesized by the combustion synthesis method was quite stable for the steam reforming of methanol.