The aim of the work is to present the XPS and UPS studies of a new kind of material MBE grown -CdYbTe thin layers. The analysis of the valence band electron states was performed for three samples (with different Yb contents and different crystallographic quality) by means of resonant photoemission based on the electronic transition between Yb 4d–4f shells. Analysis of Cd 3d, Te 3d and Yb 4d core levels made by XPS gave the qualitative information about the samples before and after Argon ion sputtering. The photoemission spectra for the CdYbTe sample containing 5% Yb, which corresponds to the limit of Yb solubility, were compared with the spectra of the CdYbTe sample with 1% Yb. By means of resonant photoemission Ytterbium was found in two charge states Yb(+2) and Yb(+3).