The effect of calcium peroxide (CaO2), zinc oxide (ZnO), copper oxide (CuO), and calcium carbonate (CaCO3) as additives during the anaerobic co-digestion of food waste and cow dung is experimentally investigated to enhance the hydrogen fermentation. The maximum concentration of hydrogen in the generated gas is found to be 26.43%, 21.67%, 17.64%, and 20.84% while the cumulative yield of hydrogen remains 114.1, 109.27, 104.87, and 107.38 mL g− 1 Total Solid (TS) with CaO2, ZnO, CuO, and CaCO3 respectively. The sample in which no additive is used (control) exhibits a maximum hydrogen concentration of 17% and a cumulative hydrogen generation of 101.57 mL g− 1 TS in the produced gas. Result reveals an enhancement in the hydrogen concentration up to 9.43% whereas the cumulative hydrogen yield is increased up to 11% with additives compared to the control sample. Overall the hydrogen fermentation can be significantly enhanced with the additives through the anaerobic co-digestion process.