Chemical shifts of SKα, CrKβ1,3 and SnLβ2 were precisely measured with a two-crystal X-ray spectrometer (Toshiba AFV 701). Sulfur in the coke for iron smelting takes two oxidation states, i.e., S2− and S6+. Quantitative analyses of S2− and S6+ were performed by precisely measuring the profile of SKα and fitting the standard S2− of S6+ curve to the observed SKα profile with the non-linear least square method. Chemical shifts of CrKβ1,3 and SnLβ2 were utilized for the determinations of Cr6+, Cr3+, Sn4+ and Sn2+ in electro-plating solutions. Intensity ratio of IA to Ig was measured, where B means the point which showed an intensity independent of oxidation states. A means the point which showed the most dependent. Linear relations were found between intensity ratio IA/IB and Cr3+/Cr or Sn2+/Sn.