Satellite structures detected in Cr3s, Cr3p core-levels and valence band X-ray photoelectron spectra of CrCl 3 insulators have been discussed within the cluster model approach. It turns out that the effective hybridisation (T eff ≅3.7 eV) can be sufficient to account for the main peak-satellite splitting in the valence band region. The photoconductivity band gap in CrCl 3 is essentially of d–d type, although the Cr 3d main emission may be due to weakly mixed 3d 2 and 3d 3L 1 final state configurations. However, although the intrinsic satellite structure in Cr3s and Cr3p core levels may originate from a charge transfer process, competition with the exciton mechanism for the origin of satellites should be considered, when the satellite energy distance from the main line becomes large.