The construction of highly active centers over the CeO2-based catalyst for the low-temperature NH3 selective catalytic reduction of nitrogen oxides (NH3–SCR) technology in non-power industry is one of the challenges in the application field. Herein, the SCR performance of MoO3/CeO2 catalyst has been remarkably enhanced by introducing Cu to induce the generation of active MoO structure. Advanced spectroscopy characterizations reveal that the adding of Cu into MoO3/CeO2 catalyst could create unsaturated sites on CeO2 for Mo anchor, and the enhanced electrons transfer from Mo to Cu would cause the formation of a new terminal MoO with highly distorted octahedral geometry, which is a new Lewis acid site for coordinated NH3 production. Meanwhile, the added Cu creates the adsorbed site for gaseous NO and the formed Mo-O-Cu pair center facilitates the transformation of ionic NO2– generated from NO adsorption to NO2, which is conducive to the fast SCR reaction process.