The electrocatalytic nitrogen reduction reaction (NRR) is a promising approach for renewable ammonia synthesis but remains significantly challenging due to the low yield and poor selectivity. Herein, a facile N and S dual anions substitution strategy is developed to tune the Ti oxidation states of TiO2 nanohybrid catalyst (NS‐TiO2/C), in which anatase TiO2 nanoplates with dense Ti3+ active sites are uniformly dispersed on porous carbon derived from 2D Ti3C2Tx nanosheets. The catalyst NS‐TiO2/C exhibits a superior ambient NRR efficiency with an NH3 yield rate of 19.97 µg h−1 mg−1cat and Faradaic efficiency of 25.49% and is coupled with a remarkable 50 h long‐term stability at −0.25 V versus RHE. Both experimental and theoretical results reveal that the N and S dual‐substitution effectively regulate the Ti oxidation state and electronical properties of the NS‐TiO2/C via simultaneously forming interstitial and substitutional TiS and TiN bonds in the anatase TiO2 lattice, inducing oxygen vacancies and dense Ti3+ active species as well as better electronic conductivity, which substantially facilitates N2 chemisorption and activation, and reduces the energy barrier of the rate‐determining step, thereby essentially boosting NRR efficiency. This work provides a valuable approach to the rational design of advanced materials by modulating oxidation states for efficient electrocatalysis.
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