Recently, metal-–organic frameworks (MOFs) with high porosity have drawn extensive attention in water splitting. The present study reports the synthesis of a porous Fe-based MOF by a modified precursor made of magnetite (Fe3O4). Subsequently, a series of undoped and lanthanide -doped (MOFs) are prepared using the solvothermal method. The synthesis provided a high surface area with a high specific surface and pore volume. The synthesized electrocatalyst with a high surface area is demonstrated as an excellent electrocatalyst for the hydrogen evolution reaction (HER) investigated in acidic media. The electrochemical results demonstrated low Tafel slopes (81 and 166 mV dec–−1), high exchange current, high ssurface area (Cdl) (148.29 and 150.57 mV), and high stability for Au/MIL-53 (Fe)/Gd-Fe3O4 and glassy carbon electrode GCE/MIL-53 (Fe)/La-Fe3O4. The high activity is attributed to the large surface area of the synthesized Fe/ Fe3O4-based MOF, which is porous and magnetic. The effect of base metal on catalyst performance was discussed. Through the unification of two catalytically active metals as lanthanide, a new opportunity opens up for the development of synergistic systems in multiple applications.