Abstract: | Efficient utilization of methane via catalytic complete combustion is a very important pathway to realize energy efficiency and pollution reduction. From the viewpoint of structural design, herein a green water‐phase route is developed to prepare ultrathin Co(OH)2 nanosheet supported Pd catalysts. As a platform, the as‐obtained Pd/Co(OH)2 nanosheets are able to be further used to load CeO2 nanoparticles to form 2D nanostructured Pd/CeO2/Co(OH)2 multicomponent hybrids, and further calcination can result in the final well‐crystallized ultrathin Co3O4 nanosheet supported PdO/CeO2 catalysts. Catalytic tests on methane combustion reveal that CeO2 as a catalytic assistant greatly boosts the catalytic performance of PdO/Co3O4 via strong synergetic effects with Pd species and Co3O4 components. The best sample of PdO/CeO2‐0.1/Co3O4 exhibits surprisingly enhanced light‐off activity, indicating that such 2D Co3O4 nanosheet supported nanocatalysts might show promising prospect for heterogeneous catalysis. |