Decomposition reactions of NaClO3, KClO3, and KIO4induced by 3 keV Ar+ions and 1254 eV X-rays are investigated by X-ray photoelectron spectroscopy (XPS). The reactions lead to the formation of binary halides with preferential losses of oxygen. The decomposition pattern, monitored at the various stages of reaction, indicates almost direct changeover to the final products with only a few intermediate species formed. Product abundancies are compared for the ion, X-ray, and electron induced reactions and discussed in relation to the various radiation induced reaction mechanisms.