The aim of this study was to develop efficient anode materials for direct methanol fuel cell applications. The Ni foam was modified with Bi2O3 - acetylene black-rGO to increase catalytic activity toward methanol oxidation. The Bi2O3 was synthesized via a straightforward green technique. The characterization was achieved by using Fourier transform infrared spectroscopy and X-Ray diffraction analysis. The transmission electron microscope and field emission scanning electron microscope was utilized to evaluate the surface properties of catalysts, and energy-dispersive X-ray spectroscopy were employed to determine the chemical composition. Bi2O3 particles with diameters ranging from 15 to 75 nm were crystal structures in the (111), (220), (311), and (342) crystal planes. The performance of methanol electrooxidation in an alkaline medium was investigated using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques. The surface coverage of the redox species was 2.04 × 10−5 mol g−1, and the diffusion coefficient ranged between 8.02 × 10−12 and 1.25 × 10−13 cm2 s−1. According to the obtained results, the Bi2O3 - acetylene black-rGO modification enhanced the electrocatalytic activity of Ni foam against methanol oxidation in an alkaline medium. •This research aimed to produce effective anode materials for methanol fuel cells.•Facile method was used to generate composite electrocatalyst.•Bi2O3- acetylene black-reduced graphene oxide supported Ni foam used.