Quantitative valence analysis of iron included in synthesized glasses has been carried out by using high-resolution X-ray fluorescence (XRF) analyzer which attached the high-resolution curved-double analyzing crystals of Si(220). The measurement results of the standard materials of Fe²⁺ (FeTiO₃) and Fe³⁺ (Fe₂O₃) have been carefully compared for the peak analysis of provided high-resolution Fe-K_α profiles. The chemical valences (Fe²⁺ and Fe³⁺) of iron component included in the glasses have been quantitatively analyzed on the basis of multiple peak analysis of Fe-K_α (both Fe-K_α1 and Fe-K_α2). The Fe²⁺/Fe³⁺ ratio has been calculated for the glasses which were synthesized under the different oxidation–reduction conditions. Additionally, the quantitative valence analysis of sulfur has been also carried out by using high-resolution XRF analyzer which attached the analyzing crystals of Ge(111) in order to clarify the relationships with iron component. Chemical valences (S²⁻ and S⁶⁺) of sulfur component were congruent with the chemical valence of iron component. Quantitative valence analysis by high-resolution XRF analysis has large advantages for the sample preparations, the surface analysis and the automated analysis.