Interfaces between active metal and metal oxide in a heterogenous catalyst often play an important role in catalysis. In this work, we intentionally synthesized a series of inverse CeO₂-Cr₂O₃/Ni model catalysts with the formation of controlled CeO₂-Ni and Cr₂O₃-Ni interfacial structures and investigated the roles of the oxide-metal interfaces in CO₂ methanation performance through excluding the normal support effect. Experimental and DFT calculation results reveal that the formate pathway tends to occur on the catalyst with only CeO₂-Ni interfaces. The Cr₂O₃-Ni interface formed after introducing Cr oxide alters the nearby CeO₂-Ni interface by electron transfer through Ni, which brings an additional reaction pathway (CO pathway) on CeO₂-Cr₂O₃/Ni. Furthermore, it shows a relatively lower CO₂ absorption energy and activation energy barrier for CO₂ dissociation to CO at the Cr₂O₃-Ni interface, favorable for CO₂ activation and further hydrogenation, thus leading to excellent low-temperature activity.