A novel Ni-MOF/nickel disulfide heterojunction composite (Ni-BTC/NiS 2 ) has been constructed successfully via in situ self-assembly strategy for the first time, which exhibits excellent MOR activity and durability. • A heterojunction composite has been constructed via in situ self-assembly strategy. • Ni-BTC/NiS 2 composite exhibits excellent electrocatalytic properties for MOR. • This work provides a new vision for the design of MOR electrocatalysts. Nickel-based metal-organic frameworks (Ni-MOFs) are a promising anodic electrocatalyst for methanol oxidation reaction (MOR), but suffer from either low conductivity or poor chemical stability. The fabrication of MOF-based heterogeneous composites is one of the possible solutions. Herein, for the first time, a novel Ni-MOF/nickel disulfide heterojunction composite (Ni-BTC/NiS 2 ) has been constructed successfully via in situ self-assembly strategy, which exhibits excellent MOR activity and durability with an area specific peak current density of 34.36 mA cm −2 . The enhanced electrocatalytic performance of the composite might be attributed to the synergistic/interface effect derived from the heterojunction structure. Undoubtedly, the integration of MOFs and inorganic functional species within a heterostructure realized by this work provides a new vision for the design of MOF-based electrocatalysts for MOR and other energy conversion processes.