Chemical shift, differences of full width at half maximum (ΔFWHM) and full width at half maximum (FWHM) of Kα and Kβ1,3 x-ray emission lines were measured for the following Co compounds: Co, CoO, Co2O3, CoSO4.7H2O, Co(NO3)2.6H2O, CoCr2O4, Co(ClO4)2.6H2O, Co(C2H3O2), CoCl2.6H2O, CoCl2, CoF2, CoF2.4H2O 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 Kβ1,3 lines than Kα ones. It should be noted that the magnitude of chemical shifts increases with the increasing number of ligand atoms.