© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The electrochemical nitrogen reduction reaction (NRR) is a promising energy-efficient and low-emission alternative to the traditional Haber–Bosch process. Usually, the competing hydrogen evolution reaction (HER) and the reaction barrier of ambient electrochemical NRR are significant challenges, making a simultaneous high NH3 formation rate and high Faradic efficiency (FE) difficult. To give effective NRR electrocatalysis and suppressed HER, the surface atomic structure of W18O49, which has exposed active W sites and weak binding for H2, is doped with Fe. A high NH3 formation rate of 24.7 μg h−1 mgcat−1 and a high FE of 20.0 % are achieved at an overpotential of only −0.15 V versus the reversible hydrogen electrode. Ab initio calculations reveal an intercalation-type doping of Fe atoms in the tunnels of the W18O49 crystal structure, which increases the oxygen vacancies and exposes more W active sites, optimizes the nitrogen adsorption energy, and facilitates the electrocatalytic NRR.