To improve the ignitability of high energy aluminum powder, in this study, natural oxide films (alumina, Al2O3) were chemically removed and nickel coatings were deposited using an electroless method for nickel plating. The time-dependent degree of nickel deposition was confirmed qualitatively and quantitatively through surface analysis using scanning electron microscopy/energy dispersive spectroscopy. To characterize the nickel coatings, we also conducted elemental analysis by using X-ray diffraction and weight analysis by using inductively coupled plasma optical emission spectrometry. Thermophysical studies were also conducted using thermogravimetric analysis/differential scanning calorimetry in an air-oxidized environment. The results of these analyses explain the ignition enhancement mechanism observed in the nickel-coated aluminum powder. A novel plating method for creating a nickel-coated aluminum powder was established and the mechanism for the enhancement of the ignition and combustion of the powder is elucidated.