Leveraging designed electronic oxide-metal interactions (EOMI), cerium-supported copper demonstrates remarkable competitiveness in the carbon dioxide reduction reaction (CO2RR). Nevertheless, the limited utilization efficiency of conventional cerium oxide (CeO2) support hampers the EOMI effect. Furthermore, a comprehensive understanding of the influence of distinct crystalline surfaces of CeO2 on the loaded active copper (Cu) species remains elusive. Herein, oxide carriers with diverse crystal facets are acquire for loading to load Cu species through the incorporation of cerium-based metal organic frameworks (MOFs) precursors. Simultaneously, owing to the elevated specific surface area conferred by MOF precursors, Cu/CeO2 hosts ample catalytically active sites for carbon dioxide (CO2) electrocatalytic reactions and as catalytic cathodes for lithium-CO2 (Li-CO2) batteries. Furthermore, the carbon converted from organic ligands in MOFs precursors not only proficiently immobilizes and disperses the active sites, but also enhances the inherent conductive stability of the oxide while augmenting energy utilization efficiency. Leveraging these advantages, the electrocatalyst derived from MOFs achieves a peak CO2-to-methane Faradaic efficiency of 57.9 %, whereas the assembled Li-CO2 batteries exhibit notable activity and durability, boasting a substantial full-discharge capacity of 8907 mAh/g, a discharge voltage of 2.65 V, and an extended cycle life exceeding 1000 h. Mechanistic investigations were conducted using density functional theory (DFT) calculations to thoroughly explore the impact of CeO2 carrier crystal facets, specifically (111), (100), and (110), on the loaded copper species. Notably, (110) was identified as the optimal facet due to its favorable contributions to electronic structure optimization and stability enhancement.