Ammonia (NH) is an essential feedstock for fertilizers and a promising carrier for carbon-free hydrogen fuel. However, its conventional production through the energy-intensive Haber-Bosch process results in significant carbon dioxide emissions. Here, we report an eco-friendly solid-state synthesis of bismuth vanadium oxide supported on treated carbon black (BiVO@CB), denoted as BV64@CB, as an efficient electrocatalyst for the nitrogen reduction reaction (NRR). This electrocatalyst exhibits exceptional activity owing to its unique coordination environment, which effectively sustains electron deficiencies. In this system, vanadium (V) active sites facilitate nitrogen (N) adsorption, while bismuth (Bi) promotes the hydrogenation of adsorbed N, leading to the formation of NNH intermediates on the BV64@CB surface. The cooperation between vanadium and bismuth enhances NRR efficiency, thereby promoting NH synthesis via the distal associative pathway. These mechanistic insights are supported by in situ X-ray absorption spectroscopy and Raman analyses. The BV64@CB electrocatalyst exhibits an impressive average NH yield rate of 370.1 μg h mg and a Faradaic efficiency of 90.94% at -0.4 V versus the reversible hydrogen electrode in a 0.2 M LiSO electrolyte (pH 5). This performance surpasses that of other bimetallic oxide electrocatalysts, underscoring its potential as an efficient and sustainable candidate for NH synthesis.