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Sheaf-like and layered CeO2with micro/nanocomposite structure were synthesized by a simple and friendly hydrothermal method and used in lean methane combustion. The relationship between the CeO2structure and catalytic performance in lean methane combustion has been studied by the means of XRD, SEM, TEM&HRTEM, H2-TPR, BET and XPS. According to the H2-TPR results, the reducibility of sheaf-like CeO2is higher compared with layered CeO2. XPS results reveal that oxygen vacancies are more easily formed on the surface of sheaf-like CeO2than that on layered CeO2surface. The catalytic activity of CeO2in lean methane combustion is strongly related to its morphology; the obtained sheaf-like CeO2with better reducibility and larger content of Ce3+exhibits much higher catalytic activity in lean methane combustion compared with the layered CeO2.Sheaf-like and layered CeO2with micro/nanocomposite structure were synthesized by a simple and friendly hydrothermal method and used in lean methane combustion. The catalytic activity of CeO2in lean methane combustion is strongly related to its morphology; the obtained sheaf-like CeO2with better reducibility and larger content of Ce3+exhibits much higher catalytic activity in lean methane combustion compared with the layered CeO2.