The electrolysis of water is considered as a potentially realistic technology for the massive production of hydrogen. The use of graphene composites in electrocatalytic water splitting has been extensively investigated. Graphene-iron oxide composites were prepared via in situ polymerization of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) and poly (ethylene glycol) monomethacrylate (PEG) on graphene surface (non-oxidative graphite-HOPG/G) in presence of iron oxide nanoparticles (IONPs) and denoted as G-INSCP. Copolymers PMPC-co-PEG (CP) and block copolymer PMPC-b-PEG (BCP) were prepared and their structures were thoroughly characterized. These polymers were used to prepare G-INSCP, G-CP, and G-BCP, their stabilities were compared and their morphologies were studied. HOPG, G-CP, and G-INSCP were used in the hydrogen evolution reaction (HER) as effective platinum catalyst alternatives. G-BCP composite was excluded owing to its very low stability. To evaluate the performance of these electrocatalysts in acidic media, linear sweep voltammetry and electrochemical impedance spectroscopy were employed. Results revealed that, compared with HOPG and G-CP, G-INSCP exhibited a significantly improved catalytic activity with respect to HER in an acidic electrolyte. Additionally, at a current density of 10 mA cm−2, G-INSCP demonstrated a lower overpotential and Tafel slope of 95 mVRHE and 67 mV dec−1, respectively. These observations were attributed to the synergistic effect between the magnetic IONPs and PMPC polymer along with the increase in the electron transfer rate owing to the conductive graphene in the catalyst. Thus G-INSCP catalyst can be a potential candidate for HER and paving the way for the advancement of new and similar catalysts for other applications.