Undoped and CeO2-doped Sro(0.5)Ba(0.5)Nb(2)O(6) (SBN) powders were synthesized using the solid-state reaction method. The lattice parameters of undoped and CeO2-doped SBN were evaluated using X-ray diffractometry. The valence state of the cerium ion in Ce-doped SBN was identified using X-ray photoelectron spectroscopy (XPS), and the valence of 3+ was confirmed. The charge-compensated defect of the cerium doping in SBN ceramics, i.e., excessive oxygen ions occupying the vacant O(4) or O(5) site, was further evidenced using electron energy-loss spectroscopy (EELS) and XPS. The relationships of charge-compensated defect, structure, binding energy, and temperature of the maximum of the relative permittivity (T-m) were discussed.