Reasonably regulating electronic coupling to promote charge transfer and exciton separation has been regarded a promising approach in catalysis. The material engineering of van der Waals heterojunction (vdWsH) based on two-dimensional (2D) materials would be a potential way to optimize the as-prepared extrinsic physicochemical characteristics. However, it was still an almost uncultivated land waiting for exploration in catalysis. Herein, we introduced the inert h-boron nitride (h-BN) in non-metal reduced graphene oxide (GN) catalysts and constructed BN-GN vdWsH. The theoretical calculation demonstrated that the h-BN can effectively modify the electronic properties of graphene. With the introduction of h-BN, the BN-GN vdWsH can obviously enhance the catalytic activity of Li-CO₂ battery. The existence of BN-GN vdWsH can reduce the overpotential more than 700 mV compared with reduced graphene oxide during the CO₂ reduction reaction (CO₂RR) and CO₂ evolution reaction (CO₂ER), and it extended cyclic stability more than three times, which was one of the most outstanding non-metallic catalysts. The reasonable structure design made it work as a high efficient electrocatalyst, which shed light on the development for functional treatment of catalytic materials.