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 Bi4 V2 O11 /CeO2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi4 V2 O11 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 Bi4 V2 O11 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 Bi4 V2 O11 /CeO2 hybrid with crystalline phase (BVC-C) counterpart.