Electronic structure of LaMo6Se8, Ce0.5Sn0.5Mo6S8, EuMo6S8 compounds known as Chevrel phases were studied by resonant photoemission spectroscopy in the energy range where RE 4f emission is selectively and locally enhanced by intershell 4d-4f transition. The PE spectra show that the intensity. of photoemission near E-F is rather high for all studied compounds that reflect the metallic character of compounds. Resonant photoemission indicates that the density of states (DOS), at the Fermi level has a small S 3p component as well as the dominant Mo 4d character with intercluster Mo 4d-S 3p hybridisation. The. valence states of Ce and La in REMo6S8 are trivalent and bivalent for the Eu compounds. The obtained experimental data were compared with. our results of LDA-LCAO band-structure calculations for LaMo6Se8 and demonstrate good agreement.