The construction of heterojunctions in composite materials to optimize the electronic structures and active sites of energy materials is considered to be the promising strategy for the fabrication of high-performance electrochemical energy devices. In this paper, a one-step, easy processing and cost-effective technique for generating composite materials with heterojunctions was successfully developed. The composite containing Ni3S4, NiS, and N-doped amorphous carbon (abbreviated as Ni3S4/NiS/NC) with multiple heterojunction nanosheets are synthesized via the space-confined effect of molten salt interface of recrystallized NaCl. Several lattice matching forms of Ni3S4 with cubic structure and NiS with hexagonal structure are confirmed by the detailed characterization of heterogeneous interfaces. The C–S bonds are the key factor in realizing the chemical coupling between nickel sulfide and NC and constructing the stable heterojunction. Density functional theory calculations further revealed that the electronic interaction on the heterogeneous interface of Ni3S4/NiS can contribute to high electronic conductivity. The heterogeneous interfaces are identified to be the good electroactive region with excellent electrochemical performance. The synergistic effect of abundant active sites, the enhanced kinetic process and valid interface charge transfer channels of Ni3S4/NiS/NC multiple heterojunction can guarantee high reversible redox activity and high structural stability, resulting in both high specific capacitance and energy/power densities when it is used as the electrode for supercapacitors. This work offers a new avenue for the rational design of the heterojunction materials with improved electrochemical performance through space-confined effect of NaCl.