Boron has been explored as p-block catalysts for nitrogen reduction reaction (NRR) by density functional theory. Unlike transition metals, on which the active centers need empty d orbitals to accept the lone-pair electrons of the nitrogen molecule, the sp 3 hybrid orbital of the boron atom can form B-to-N π -back bonding. This results in the population of the N-N π∗ orbital and the concomitant decrease of the N-N bond order. We demonstrate that the catalytic activity of boron is highly correlated with the degree of charge transfer between the boron atom and the substrate. Among the 21 concept-catalysts, single boron atoms supported on graphene and substituted into h-MoS 2 are identified as the most promising NRR catalysts, offering excellent energy efficiency and selectivity against hydrogen evolution reaction.