The restricted charge transfer and slow oxygen evolution reaction (OER) dynamics tremendously hamper the realistic implementation of SnS2 photoanodes for photoelectrochemical (PEC) water splitting. Here, a novel strategy is developed to construct interfacial NCuS bonds between NC skeletons and SnS2 (CuNC@SnS2) for efficient PEC water splitting. Compared with SnS2, the PEC activity of CuNC@SnS2 photoelectrode is tremendously heightened, obtaining a current density of 3.40 mA cm2 at 1.23 VRHE with a negatively shifted onset potential of 0.04 VRHE, which is 6.54 times higher than that of SnS2. The detailed experimental characterizations and theoretical calculation demonstrate that the interfacial NCuS bonds enhance the OER kinetic, reduce the surface overpotential, facilitate the separation of photon‐generated carriers, and provide a fast transmission channel for electrons. This work presents a new approach for modulating charge transfer by interfacial bond design in heterojunction photoelectrodes toward promoting PEC performance and solar energy application.