Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate‐determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2‐WO3 to elevate the d‐band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2‐WO3 exhibited a high NH3 yield of 62.38 μg h−1 mgcat−1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2‐WO3 upshifted the d‐band center of W towards the Fermi level, leading to enhanced adsorption of −NH2 and −NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d‐band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process. The strong interfacial electric field in WS2‐WO3 can enhance the adsorption of intermediates by elevating the d‐band center of W, resulting in an accelerated electrocatalytic nitrogen reduction reaction (ENRR) kinetics.