An Amorphous Noble‐Metal‐Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions

N2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH3 production, which still heavily relies on the Haber–Bosch process at the cost of huge energy and massive production of CO2. A noble‐metal‐free Bi4V2O11/CeO2 hybrid with an amorphous phase (BVC‐A) is used as the cathode for electrocatalytic NRR. The amorphous Bi4V2O11 contains significant defects, which play a role as active sites. The CeO2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi4V2O11 for rapid interfacial charge transfer. Remarkably, BVC‐A shows outstanding electrocatalytic NRR performance with high average yield (NH3: 23.21 μg h−1 mg−1cat., Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi4V2O11/CeO2 hybrid with crystalline phase (BVC‐C) counterpart. A fix on nitrogen: An amorphous Bi4V2O11‐crystalline CeO2 hybrid catalyst is investigated for electrocatalytic N2 fixation. The as‐obtained noble‐metal‐free catalyst possesses high amounts of defects as active sites, as well as band alignment for interfacial charge transfer, to promote the nitrogen reduction reaction.