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Creating innovative catalysts utilizing nonprecious metals for the electrocatalytic hydrogen evolution reaction (HER) poses a significant difficulty. We present a cobaloxime (Cox) complex having pyridine (2-Cox) and tetrafluorophenyl-thio-pyridine (4-Cox) functional groups, which contains a 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) moiety. This combination serves as a catalyst for proton reduction and is immobilized onto reduced graphene oxide (rGO) by π–π stacking between the cobaloxime complex and rGO. Moreover, the unique complex's structures were determined through the application of ultraviolet–visible spectroscopy (UV–Vis), Fourier Transform Infrared spectroscopy (FT-IR), X-ray diffraction spectroscopy (XRD), and scanning electron microscopy (SEM). The electrocatalytic activity of the two rGO/2-Cox and rGO/4-Cox electrodes towards hydrogen (H 2) were examined under both alkaline and acidic conditions. The cobaloxime-modified rGO electrodes demonstrate superior electrocatalytic performance for the HER under acidic conditions compared to alkaline conditions. The overpotential at a current density of 10 mA cm−2 for rGO/2-Cox in 0.5 M H 2 SO 4 is −0.342 V, which is notably lower than the overpotential of rGO/4-Cox (−0.496 V). The Tafel slope for the rGO/2-Cox electrode in a 0.5 M H 2 SO 4 solution is 111 mV.dec−1, but for the rGO/4-Cox electrode it is 156 mVdec−1. This discrepancy suggests that the rGO/2-Cox electrode demonstrates better performance in the HER compared to the rGO/4-Cox electrode. • Two different BODIPY-cobaloxime complexes were synthesized. • These combinations are immobilized on reduced graphene oxide by π-π stacking. • The electrocatalytic activity of these structures towards hydrogen was studied. • 2-Cox structure exhibited superior electrocatalytic performance for HER. • These catalysts have the potential to be used in various energy applications. [ABSTRACT FROM AUTHOR]