Heterojunction photocatalysts at present are still suffering from the low charge separation/transfer efficiency due to the poor charge mobility of semiconductor-based photocatalysts. Atomic-scale heterojunction-type photocatalysts are regarded as a promising and effective strategy to overcome the drawbacks of traditional photocatalysts for higher photoenergy conversion efficiencies. Herein, an atomic-scale heterojunction composed of a boron nitride monolayer and graphene (h-BN-C/G) is constructed to significantly shorten the charge transfer path to promote the activation of molecular oxygen for artificial photosynthesis (exemplified with oxidative coupling of amines to imines). As the thinnest heterojunction, h-BN-C/G gives the highest conversion, which is eightfold higher than that of the mechanical mixture of graphene and boron nitride monolayers. h-BN-C/G exhibits a high turnover frequency value (4.0 mmol benzylamine g-1 h-1), which is 2.5-fold higher than that of the benchmark metal-free photocatalyst in the literature under even critical conditions.