X-ray photoelectron spectroscopy is employed to study inner-shell core-level binding energies Eu 4d, Ti 2p and O 1s, Ba 3d for new single-phase Ba1-xEuxTiO3 (0.1 <= x <= 0.4) samples prepared by solid state reaction at 4.0 GPa and 1090 degrees C. The peak positions of binding energies determined by linear background subtraction and Gaussian fit are presented. XPS analysis indicates that the mixed-valent Eu3+/Eu2+, ions at A-site and Ti4+/Ti3+ ions at B-site coexisted in the Ba1-xEuxTiO3 powder surface, and the amount of Eu2+ ions is equal to Eu3+ ions. Published by Elsevier B.V.