MoS2 ultrathin nanosheet-coated CeO2 hollow sphere (CeO2@MoS2) hybrid nanostructures with a 3D hierarchical configuration were successfully constructed from a facile two-step wet chemistry strategy: first, CeO2 formed on a silica core which served as a template and was subsequently removed by NaOH solution to attain hollow spheres, and then few-layered ultrathin MoS2 nanosheets were deposited on the CeO2 hollow spheres through a hydrothermal process. As a proof of concept application, the as-prepared CeO2@MoS2 hybrid nanostructures were used as catalytic material, which exhibited enhanced catalytic activity in ammonia decomposition for H2 production at high temperature. It was demonstrated that, even with a structural transformation from MoS2 to MoNx under harsh conditions of ammonia decomposition at high temperature (700 °C), the 3D hierarchical nanostructures of the CeO2@MoNx were well kept, indicating the important role of the CeO2 support.