In this study, K-beta-to-K-alpha X-ray intensity ratios of Ni in Ni-B alloy coatings were investigated. These samples were excited by 59.5 keV gamma-rays from a Am-241 annular radioactive source. K X-rays emitted by the samples were counted using an Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV. The K-beta-to-K-alpha X-ray intensity ratios of Ni-B alloys are compared with pure Ni and each other. Deviations between the results were explained by the change in valence electronic structures of Ni in Ni-B alloy coatings.