The energy band gap, the band alignment with Si, and the chemical bonding of 4-5 nm thick (TbxSc1-x)2 O3 dielectric films were investigated as a function of composition. Films with x=0, 0.5, and 1 were prepared by a molecular beam deposition technique on silicon substrates. The structure of the dielectric films was characterized by high resolution transmission electron microscopy. We found that upon deposition, a silicate and a silicon oxide layer were formed at the dielectric/silicon interface for all compositions. X-ray photoelectron spectroscopy was used to determine the band gap, as well as the energy band alignment with Si and the chemical structure of the films. Energy gap values of 6.0±0.2 and 7.5±0.2 eV were obtained for pure Sc2O3 and Tb 2 O3, respectively, while for the mixed layer (x=0.5) a value of 6.8±0.2 eV was extracted. It was found that the valence band offset does not change with Sc addition to Tb2O3, while the conduction band offset increases with x, from a value of 2.9±0.2 eV for the x=0 (pure Sc2O3) to a value of 5.7±0.2 eV for x=1 (pure Tb2O3).