Various CeCoOx mixed-oxide catalysts with different Ce/Co ratios were prepared by surfactant-assisted template precipitation of CeO2 and Ce3O4. The obtained catalysts were characterized by X-ray diffraction, X-ray photoelectron spectra, hydrogen temperature-programmed reduction, nitrogen physisorption, and transmission electron microscopy. In general, the mixed-oxide CeCoOx catalysts showed well-dispersed CeO2 and Co3O4 and good catalytic characteristics including a high specific surface area and porous structure. The effectiveness of the prepared catalysts on the hydrogen (H-2) production from steam reforming of fusel oil was studied in a packed-bed reactor. Co played an important role in C-C scission to break down the large C2-5 molecules into smaller species resulting in H-2 formation. Ce could provide supplementary active oxygen to prevent coke formation on Co, resulting in a more stable activity of the mixed-oxide catalyst throughout the reaction course.