The dry reforming of methane provides an attractive route to convert greenhouse gases (CH and CO) into valuable syngas, so as to resolve the carbon cycle and environmental issues. However, the development of high-performance catalysts remains a huge challenge. Herein, we report a 0.6% Ir/CeO catalyst with a metal-support interface structure which exhibits high CH (72%) and CO (82%) conversion and a CH reaction rate of ~973 μmol g s which is stable over 100 h at 700 °C. The performance of the catalyst is close to the state-of-the-art in this area of research. A combination of in situ spectroscopic characterization and theoretical calculations highlight the importance of the interfacial structure as an intrinsic active center to facilitate the CH dissociation (the rate-determining step) and the CH* oxidation to CHO* without coke formation, which accounts for the long-term stability. The catalyst in this work has a potential application prospect in the field of high-value utilization of carbon resources.