Electrocatalytic N₂ reduction under ambient conditions is a promising alternative to the traditional Haber–Bosch process for environmentally benign and sustainable NH₃ production but requires efficient electrocatalysts for the N₂ reduction reaction (NRR). Here, we report that metal–organic framework-derived shuttle-like V₂O₃/C acts as an outstanding NRR electrocatalyst for N₂-to-NH₃ conversion with excellent selectivity under ambient conditions. In 0.1 M Na₂SO₄, such V₂O₃/C exhibits a remarkable NH₃ yield of 12.3 μg h⁻¹ mg⁻¹_cat. and a high faradaic efficiency of 7.28% at a potential of −0.6 V versus reversible hydrogen electrode, outperforming most of the reported aqueous-based NRR electrocatalysts. Notably, it also shows high electrochemical and structural stability.