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Renewable harvesting of clean energy using the benefits of multi-metallic catalytic materials of high entropy alloy (HEA, equimolar Cu–Ag–Au–Pt–Pd) from formic acid with minimum energy input has been achieved in the present investigation. The synergistic effect of pristine elements in the multi-metallic HEA drives the electro-oxidation reaction towards non-carbonaceous pathway. The atomistic based simulations based on DFT rationalize the distinct lowering of the d-band center for the individual atoms in the HEA as compared to the pristine counterparts. Further this catalytic activity of the HEA has also been extended to methanol electro-oxidation to show the unique capability of the novel catalyst. The nanostructured HEA, prepared using a combination of casting and cryomilling techniques can further be utilized as the fuel cell anode in the direct formic acid/methanol fuel cells (DFFE).