As the efficient approaches for obtaining clean H-2 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 (Co-0/Co2+/Co3+ and Ni2+/Ni3+) and graphene-like nanostructures embedded with abundant CoNi alloy nanoparticles. Compared with the sole-metal MOFs (Co-3(HAB)(2) MOF and Ni-3(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) (eta(10)) and Tafel slopes toward hydrogen evolution reaction (eta(10) = 119 mV, Tafel slope = 46 mV dec(-1)) and oxygen evolution reaction (eta(10) = 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 threeand 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 multi-functional electrocatalysts with boosted electrocatalytic activities in energy fields. (C) 2020 Elsevier Inc. All rights reserved.