Ceria with surface solid frustrated Lewis pairs (FLPs), formed by regulating oxygen vacancies, demonstrate remarkable ability in activating small molecules. In this work, we extended the application of FLPs on CeO2(110) to the selective catalytic reduction of NO by NH3 (NH3-SCR), finding a notable enhancement in performance compared to ordinary CeO2(110). Additionally, an innovative approach involving H2 treatment was discovered to increase the number of FLPs, thereby further boosting the NH3-SCR efficiency. Typically, NH3-SCR on regular CeO2 follows the Eley-Rideal (E-R) mechanism. However, density functional theory (DFT) calculations revealed a significant reduction in the energy barriers for the activation of N-O and N-H bonds under the Langmuir-Hinshelwood (L-H) mechanism with FLPs present. This transition shifted the reaction mechanism from the E-R pathway on regular R-CeO2 to the L-H pathway on FLP-rich FR-CeO2, as corroborated by the experimental findings. The practical application of FLPs was realized by loading MoO3 onto FLP-rich FR-CeO2, leveraging the synergistic effects of acidic sites and FLPs. This study provides profound insights into how FLPs facilitate N-H/N-O bond activation in small molecules, such as NH3 and NO, offering a new paradigm for catalyst design based on catalytic mechanism research.