This research outlines a novel designed nanocomposite (Ca2Mn3O8/CaMn3O6/MMT) for electrochemical hydrogen storage with highlight on the improve condition to attain higher performance. Ca2Mn3O8/CaMn3O6/MMT nanocomposites were prepared by loading different ratios of the Ca2Mn3O8/CaMn3O6 (5%, 10% and 25%) inside the montmorillonite K10. Electrochemical properties of the samples - montmorillonite K10, Ca2Mn3O8/CaMn3O6 and the respective nanocomposites - were considered by chronopotentiometry charge–discharge techniques in KOH medium. The Ca2Mn3O8/CaMn3O6 as additive were fabricated by a sol-gel route in the presence of various amino acids as both fuel and capping agent (glycine, alanine and leucine). The influence of amino acids on the morphology and purity of as-synthesized samples were studied by different analysis methods. The K10 montmorillonite (K10 MMT) functionalized with silane groups using (3-Aminopropyl) triethoxysilane (APTES) agent to link with nanoparticles. Fabricated Ca2Mn3O8/CaMn3O6/MMT nanocomposites applied as active material in the hydrogen storage system. Effect of weight percent of Ca2Mn3O8/CaMn3O6 nanoparticles in the K10 MMT matrix investigated in terms of hydrogen storage capacity. The discharge capacity for Ca2Mn3O8/CaMn3O6 nanoparticles and K10 MMT measured 552 and 140 mAhg−1 respectively. However, the discharge capacity for Ca2Mn3O8/ CaMn3O6/MMT nanocomposites with weight percent of 5, 10 and 25% nanoparticles in 2 M KOH calculated about 185, 316 and 269 mAhg−1 at current of 1 mA respectively. According to the obtained results, the Ca2Mn3O8/CaMn3O6/MMT nanocomposites with 10% nanoparticles on the MMT surface affirmed optimized capacity for hydrogen storage systems by cooperation of spillover, redox and physisorption mechanisms.