Chemical shifts of titanium L edges and oxygen K edges in electron energy-loss spectroscopy in transmission electron microscopy were used to detect valence state reduction of Ti in bulk barium titanates, used as reference materials, and in (BaxSr1−x)Ti1+yO3+z (BST) thin films grown with excess Ti. A hollandite-type Ba titanate, containing Ti with an average valence state of approximately 3.7 in octahedral coordination, showed large chemical shifts relative to rutile TiO2 and BaTiO3, containing only Ti4+. In BST, chemical shifts relative to BaTiO3 were measured from grain interiors of columnar films with different amounts of excess Ti. We found that shifts, corresponding to an average valence state of Ti smaller than nominal 4+, increase with increasing amounts of excess Ti in the films. The results show that at least some amount of excess Ti is accommodated in these films by a defect mechanism that requires a reduction of the average valence state of Ti. © 2001 American Institute of Physics.