A series of semiconductive CoNi bimetal–organic frameworks (CoxNi3-x(HAB)2 MOFs) were explored as the potential of the MOFs as efficient multifunctional electrocatalysts for the non-Pt methanol oxidation reaction (MOR) and overall water splitting in alkaline medium. Display omitted As the efficient approaches for obtaining clean H2 energy, methanol oxidation (MOR) and water over slitting reactions have been increasingly essential. A series of novel semiconductive CoNi bimetal–organic framework (CoxNi3-x(HAB)2 MOF) have been prepared using hexaaminobenzene (HAB) as an organic linker. The obtained series of CoxNi3-x(HAB)2 MOFs were then explored as efficient multifunctional electrocatalysts for the non-Pt MOR and overall water splitting in alkaline medium. The basic characterizations of CoxNi3-x(HAB)2 MOFs revealed that they comprised multiple metal valence states (Co0/Co2+/Co3+ and Ni2+/Ni3+) and graphene-like nanostructures embedded with abundant CoNi alloy nanoparticles. Compared with the sole-metal MOFs (Co3(HAB)2 MOF and Ni3(HAB)2 MOF), the CoxNi3-x(HAB)2 MOF with a mass ratio of Co:Ni = 1:3 (CoxNi3-x(HAB)2 MOF-2) exhibited superior electrocatalytic performance for MOR. It gave a high current density of 92.8 mA cm−2 at 1.6 V vs. reversible hydrogen electrode (RHE) for MOR, along with the low overpotentials at the current density of 10 mV cm−2 (η10) and Tafel slopes toward hydrogen evolution reaction (η10 = 119 mV, Tafel slope = 46 mV dec-1) and oxygen evolution reaction (η10 = 1.35 V, Tafel slope = 26 mV dec−1). The analysis on the catalysis mechanism of MOR and water splitting in alkaline medium was also proposed. The voltages applied to the three- and two-electrode systems based on the bifunctional CoxNi3-x(HAB)2 MOF-2 catalyst for overall water splitting are 1.52 V vs. RHE and 1.45 V vs. silver/silver chloride (Ag/AgCl), respectively. This work provides a novel strategy for investigating the applications of promising two-dimensional semiconductive MOF as multifunctional electrocatalysts with boosted electrocatalytic activities in energy fields.