FexZn1-x alloys were electrochemically deposited on aluminum substrates from a sulfate bath. The K beta/K alpha x-ray intensity ratios of Zn and Fe in FexZn1-x thin films have been experimentally studied. The energy dispersive x-ray fluorescence (EDXRF) technique was used to measure K x-ray photons. Samples were excited by using 59.5 keV photons emitted by a 50 mCi Am-241 radioactive source. The emitted K x-rays were detected by an Ultra-LEGe detector having a resolution of 150 eV at 5.9 keV. In addition, the effect of bath composition on the phase structure was investigated by x-ray diffraction (XRD) analysis. The composition of the thin films was analyzed by atomic absorption spectrometry analysis. Iron content was shown to strongly affect the structure of Zn-Fe alloys. It was found that the K-shell x-ray intensity ratio changed in FexZn1-x thin films for different values of x. The reason for this change may be that the electronegativity of iron is higher than that of zinc and that electron transfer from zinc to the outermost orbital of iron occurs. In conclusion, in FexZn1-x thin films, intensity ratio increases with increasing concentration of Zn but decreases with increasing concentration of Fe.