As of the present time, the in-depth study of the structure-activity relationship between electronic configuration and CO2 photoreduction performance is often overlooked. Herein, a series of Cux species modified CeO2 nanodots are constructed in situ by flame spray pyrolysis (FSP) to achieve an efficient photocatalytic CO2-to-C2 conversion with an electron utilization of up to 142.5µmol g-1. Through an in-depth study of the electronic behavior and catalytic pathways, it is found that the Cu0/Cu+ species in the coexistence state of Cu0/Cu+/Cu2+ can optimize the energy band structure, photocurrent stability, and provide a kinetic basis for the active surface catalytic reaction process that requires the conversion of multiple electrons into C2 products, which ultimately enhances the CO2-to-C2H6 photoreduction by 3.8-fold and that for CO2-to-C2H4 photoreduction by 5.2-fold. Besides, the Cu2+ species in the coexistence state of Cu0/Cu+/Cu2+ are able to regulate the electronic behavior and the choice of the catalytic pathway, enabling the transitions between CO2-to-C2H6 and CO2-to-C2H4. This work indicates that electronic configuration optimization is an effective strategy to significantly enhance the CO2 photoreduction performance and provides new ideas for the design and synthesis of high-performance heterostructure photocatalysts.