Well tuning the preparation, formulation and conditions applied, different series of nickel based nano-oxyhydride (Ni-Ce-O and Ni-Mg-Al-O based) catalysts were developed for the highly efficient and sustainable H2 formation from ethanol in the presence of oxygen and water at room temperature. Once in situ treated in H2 at adequate temperature, the nickel based mixed oxides become oxyhydrides, with the presence of hydrogen species of hydride nature in the anionic vacancies of the mixed oxides. The insertion into the solid of hydride species is well shown by Inelastic Neutron Scattering (INS). By taking advantage of the chemical energy released from the reaction between nano-oxyhydride catalysts and O2, continuous complete conversion of ethanol specifically at 50°C (oven temperature), with simultaneously production of H2, can be obtained. The sustainable process can be explained by a mechanism involving a heterolytic abstraction of hydride species from ethanol regenerating the oxyhydride catalyst.