A large quantity of CH4 is discharged from exhaust gas in China every year, which causes serious environmental pollution of atmosphere. Catalytic combustion is considered as one of the most effective ways to remove methane due to its low operating temperature and high efficiency. Herein, three catalysts, CuO-CeO2, CuO and CeO2, were prepared by sol-gel method to investigate the catalytic combustion activity of CH4 under (1% CH4, 78% N2 and 21% O2) atmosphere. The physical structure and surface properties were characterized using XRD, XPS, H2-TPR and O2-TPD techniques, etc. The results show that Ce ions not only promote the dispersion of Cu on the catalyst surface, but also the conversion between trivalent (Ce3+) and tetravalent (Ce4+) improves the oxygen storage and release capacity of the catalyst, which is beneficial for CuO-CeO2 to improve the catalyst activity. The evaluation of catalyst activity provides evidence that the activity order of the three catalysts follows the order CuO-CeO2>CuO>CeO2. Then, the most active CuO-CeO2 catalyst is employed to further investigate kinetic partial pressure experiment and reaction mechanism to determine the reaction rate of methane at different oxygen/methane partial pressure ratios. The results indicate that the reaction follows the L-H mechanism, that is, the adsorbed CH4 reacts with the adsorbed O2. Based on in-situ infrared spectra analysis, the microscopic reaction mechanism of CH4 over CuO-CeO2 catalyst is proposed: CH4 is firstly adsorbed on the surface of CuO-CeO2 and then reacts with CuO-CeO2 to produce intermediate products methoxy substance (Cu-OCH3) and formate substance (Cu-OOCH). Finally, the intermediate products are decomposed into CO2 and H2O to achieve the purpose of the complete oxidation.