The Ka,, 2 , KO1, 3 , KO,, and KP" emission spectra of vanadium in the element and several V(III), V(IV), and V(V) compounds have been measured with a two-crystal X-ray spectrometer. The Kal and KP1,3 peaks shift slightly to lower energies with increasing the oxidation state of vanadium atom and the K& peak shifts to higher energies with it. An approximately linear relationship between Kal width and Kal / K a 2 intensity ratio can be used for identification of vanadium oxidation state.