Abstract N 2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH 3 production, which still heavily relies on the Haber–Bosch process at the cost of huge energy and massive production of CO 2 . A noble‐metal‐free Bi 4 V 2 O 11 /CeO 2 hybrid with an amorphous phase (BVC‐A) is used as the cathode for electrocatalytic NRR. The amorphous Bi 4 V 2 O 11 contains significant defects, which play a role as active sites. The CeO 2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi 4 V 2 O 11 for rapid interfacial charge transfer. Remarkably, BVC‐A shows outstanding electrocatalytic NRR performance with high average yield (NH 3 : 23.21 μg h −1 mg −1 cat. , Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi 4 V 2 O 11 /CeO 2 hybrid with crystalline phase (BVC‐C) counterpart.