AbstractConverting CO2 under mild conditions by employing semiconductor photocatalysts is promising to address global environmental issues. However, the current CO2 conversion efficiency is limited by the difficulty activating the thermodynamically stable CO2 molecules. Constructing plasmonic nanoalloy‐based photocatalytic systems with significant localized surface plasmon resonance (LSPR) is full of potential but remains a vast challenge. In this work, AuAg plasmonic nanoalloys were incorporated on CeO2 nanorods (designated as AuAg–CeO2) to achieve selective photoreduction of CO2. The result displays that Ag can serve as a superior electron modifier to promote the electron enrichment of Au, thus producing asymmetric charge distributions to boost the selective conversion of CO2. Furthermore, the improved LSPR effect on AuAg–CeO2 induces the generation of high‐energy hot electrons under irradiation, enhancing the reactivity of electrons for CO2 photoreduction. Due to the aforementioned effects, AuAg–CeO2 exhibits a high CO2‐to‐CH4 performance of 92.6 μmol g−1 through a 3‐h test and a high CH4 selectivity of 94.5%, up to 2.6, 8.7, and 17.1 times higher than the activity of Au–CeO2, pure CeO2, and Ag–CeO2, respectively. This work can provide a new perspective for constructing high‐performance catalysts for photocatalytic CO2 reduction.