The construction of a surface-frustrated Lewis pairs (SFLPs) structure is expected to break the single electronic state restriction of catalytic centers of P-region element materials, due to the existence of acid-base and basic active canters without mutual quenching in the SFLPs system. Herein, we have constructed eight possible SFLPS structures on the Insub.2Osub.3 (110) surface by doping non-metallic elements and investigated their performance as electrocatalytic nitrogen reduction catalysts using density functional theory (DFT) calculations. The results show that P atom doping (P@Insub.2Osub.3) can effectively construct the structure of SFLPs, and the doped P atom and In atom near the vacancy act as Lewis base and acid, respectively. The P@Insub.2Osub.3 catalyst can effectively activate Nsub.2 molecules through the enzymatic mechanism with a limiting potential of −0.28 eV and can effectively suppress the hydrogen evolution reaction (HER). Electronic structure analysis also confirmed that the SFLPs site can efficiently capture Nsub.2 molecules and activate N≡N bonds through a unique “donation-acceptance” mechanism.