In order to clarify whether the mixed valence of Eu2+/Eu3+ exists in a self-compensation mode in Eu-doped BaTiO3, the site occupation and valence state of Eu ions in barium titanate were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), Raman spectroscopy (RS), and dielectric measurements. The results indicate that Eu ions may enter both Ba- and Ti-sites as Eu3+, forming a self-compensation mode with the amphoteric behavior. Self-compensation characteristics of Eu ions in BaTiO3 are reflected by an expansion in unit cell volume, evolution of the 830 cm(-1) Raman band, strong diffusion of the dielectric peak, disappearance of the Eu2+ ESR broad signal, and a g=2.004 signal independent of temperature. (C) 2011 Elsevier BM. All rights reserved.