Chemical shift and full widths at half maximum (FWHM) intensity of chromium K alpha and K beta(1,3) lines were examined for 12 kinds of materials containing chromium (CH3CO2)(7)Cr-3(OH)(2), CrK(SO4)(2)center dot 12H(2)O, Cr(NO3)(3)center dot 9H(2)O, Cr2O3, CrF2, CrF3 center dot 4H(2)O, CrCl2, CrCl3, CrCl3 center dot 6H(2)O, [CrCl2(H2O)(4)]Cl center dot 2H(2)O, Cr-2(SO4)(3)center dot 15H(2)O, CrO and Cr metal by wavelength-dispersive X-ray fluorescence (WDXRF) spectrometry. The chemical shifts, asymmetry index and the half-widths of both the X-ray emission lines show interesting trends with the oxidation state of chromium. It was observed that the chemical shifts for F compounds are higher than Cl compounds. It was also found larger chemical shifts and FWHM for K beta(1,3) lines than K alpha ones. It should be noted that the magnitude of chemical shifts increases with increase in the number of ligand atoms. Copyright (C) 2009 John Wiley & Sons, Ltd.