The paper presents photoemission studies of wide band gap semiconductors surfaces doped with gadolinium and samarium. The contribution of the Gd4f and Sm4f electrons to the electronic structure of the doped semiconductor systems (CdTe, GaN and ZnO) was evaluated based on the Fano resonance measured across the RE4d -> RE4f intra-ion photoionization threshold. It was found that the RE valence and position of the RE4f shell varies significantly between the investigated semiconductor systems and depends not only on the used semiconductor matrix but also on the Fermi level position. (C) 2013 Elsevier B. V. All rights reserved.