The methanation of CO2 is crucial for resource utilization, however, achieving excellent CO2 methanation performance with Ni-based catalysts at low temperatures remains highly challenging. In this study, a high-performance 10Ni-0.1Ce/Al catalyst was synthesized using a simple and efficient one-pot combustion method. Unlike other catalysts with the same components, this catalyst exhibits a unique feature where a small amount of the CeO2 promoter is dispersed on the support, while the majority selectively binds to and coats the Ni nanoparticles. This distinctive structure allows it to achieve approximately 80 % CO2 conversion and 99.9 % CH4 selectivity under conditions of 260 °C, 0.1 MPa, and a GHSV of 48,000 mL·g−1·h−1. The high catalytic performance is attributed to the unique structure of Ni nanoparticles and CeO2, which promotes the formation of numerous Ni-O-Ce interface active sites. These Ni-O-Ce interfaces enhance the reducibility and increase the content of weak basic sites in the catalyst. The combination of in-situ DRIFTS and TPSR reveals that the decomposition of bridged HCOO– to *CO is the rate-determining step. The presence of Ni-O-Ce interface active sites in the 10Ni-0.1Ce/Al catalyst facilitates the generation of abundant bridged HCOO– intermediates with higher activity than the 10Ni/Al catalyst, leading to a substantial enhancement in catalytic performance.