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Summary: Ammonia occupies a significant standing in the global economy. As a promising alternative to the energy-intensive Haber-Bosch process, electrochemical nitrogen reduction could achieve sustainable ammonia synthesis. However, the attractive alternative suffers from the bottleneck of insufficient activity and low electron selectivity. Here, we report an efficient electrocatalyst using phosphotungstic acid as platforms to anchor bismuth species on the 4-fold hollow site and anchor lithium species on the 3-fold hollow site, which reaches high ammonia yield rates of 61 ± 1 μg h−1 mgcat.−1 and Faradaic efficiencies of 85% ± 2% at −0.1 V versus reversible hydrogen electrode (RHE). Experiments and theoretical calculations reveal that the Biδ+ species can promote the activation and hydrogenation of nitrogen at adjacent unsaturated tungsten active sites, and the incorporated lithium species reduce the hydrogen reduction rate in undesired water splitting. This synergistic functionalization of bismuth and lithium species contributes to the high-efficient catalyst.