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• The single and double Mo anchor in biphenylene monolayer exhibit good electrical conductivity. • The exposed Mo sites in Mo 1-2 @BPN possessed positive charge could capture and activate N 2 molecules. • Electrochemical nitrogen reduction reaction on precise number of Mo atoms is systematically investigated. • Mo 1 @BPN displays a limiting potential of 0.44-0.46 V, Mo 2 @BPN exhibits a low limiting potential of 0.66 V. Electrochemical nitrogen reduction (eNRR) in ambient conditions shows intriguing prospects for ammonia generation via a simple and sustainable method. By using density functional theory studies, herein we design the precise number of Mo atoms anchored biphenylene systems. Their structures, stability, chemisorption and activation of N 2 molecules are systematically investigated. We find that the single and double Mo could stably anchor in biphenylene monolayer (Mo 1-2 @BPN). The exposed Mo sites possessed positive charge could capture and activate N 2 molecules, and promote to absorb NRR intermediates. Moreover, by controlling the number of Mo atoms, the catalytic mechanisms can be significantly adjusted. The Mo 1 @BPN monolayer prefers to the distal pathway, while Mo 2 @BPN sheet tends to the enzymatic pathway. Their corresponding low limiting potentials are 0.44 V and 0.66 V, respectively, which outperform many reported catalysts to date. These studies provide a new approach for designing highly efficient NRR electrocatalysts through precise modulation number of anchored atoms. [Display omitted] [ABSTRACT FROM AUTHOR]