Al/MoOx nanoenergetic multilayer films (nEMFs) were deposited by magnetron deposition method. The samples with bilayer thicknesses of 75 nm and 225 nm were prepared, respectively, and the total thickness is 3 μm. The as-deposited Al/MoOx nEMFs were characterized with varied analytical techniques, including SEM, XRD, XPS and DSC. Results show that the MoOx films are amorphous, and are composed of MoO3, Mo2O5 and MoO2. The values of heat release in samples are 3524 J/g and 2508 J/g, respectively, and the final products are Mo, MoO2, and Al2O3. Finally, the reaction paths and reaction kinetics of Al/MoOx exothermic reactions were discussed.