This work focuses on the sustainable green synthesis of magnetic iron oxide nanoparticles (Fe₃O₄NPs) using bioreductants derived from orange peel extracts for application in the efficient oxygen evolution reactions (OER). The synthesized catalysts were characterized using X-ray diffraction analysis, field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and UV–visible spectroscopy. The Fe₃O₄NPs exhibit a well-defined spherical morphology with a larger Brunauer–Emmett–Teller surface area and a significant electrochemically active surface area. The green synthesis using orange peel extracts leads to an excellent electrocatalytic activity of the apparent spherical Fe₃O₄NPs (diameter of 9.62 ± 0.07 nm), which is explored for OER in an alkaline medium (1.0 M KOH) using linear-sweep and cyclic voltammetry techniques. These nanoparticles achieved a benchmark current density of 10 mA cm⁻² at a low overpotential of 0.3 V versus RHE, along with notable durability and stability. The outstanding OER electrocatalytic activity is attributed to their unique morphology, which offers large surface area and an ideal porous structure that enhances the adsorption and activation of reactive species. Furthermore, structural defects within the nanoparticles facilitate efficient electron transfer and migration of these species, further accelerating the OER process.