Chemical shift, differences of full width at half maximum (Delta FWHM) and full width at half maximum (FWHM) of K alpha and K beta(1,3) x-ray emission lines were measured for the following Co compounds: Co, CoO, Co2O3, CoSO4 center dot 7H(2)O, Co(NO3)(2)center dot 6H(2)O, CoCr2O4, Co(ClO4)(2)center dot 6H(2)O, Co(C2H3O2), CoCl2 center dot 6H(2)O, CoCl2, CoF2, CoF2 center dot 4H(2)O and CoF3. The measurements were performed with wavelength-dispersive x-ray fluorescence spectrometry (WDXRF). It was found that the calculated results for Co compounds are strongly correlated with the oxidation state. At the same time, chemical shift for F compounds is generally more than that for Cl compounds. Larger chemical shifts and FWHM were also found for K beta(1,3) lines than K alpha ones. It should be noted that the magnitude of chemical shifts increases with the increasing number of ligand atoms.