In this work, the effects of Nb2O5 addition on the dielectric properties and phase formation of BaTiO3 were investigated. A core-shell structure was formed for Nb-doped BaTiO3 resulted from a low diffusivity of Nb5+ ions into BaTiO3 when grain growth was inhibited. In the case of 0.3-4.8 mol% Nb2O5 additions, two dielectric constant peaks were observed. The Curie dielectric peak was determined by the ferroelectric-paraelectric transition of grain core, whereas the secondary broad peak at lower temperature was due to strong chemical inhomogeneity in Nb-doped BaTiO3 ceramics. The dielectric constant peak at Curie temperature was markedly depressed with the addition of Nb2O5. On the other hand, the secondary dielectric constant peak was enhanced when sintered above 1280 A degrees C for higher Nb2O5 concentrations (a parts per thousand yen1.2 mol%). The Curie temperature was shifted to higher temperatures, whereas the transition temperature corresponding to the secondary peak moved to lower temperatures as increasing the amount of Nb2O5 more than 1.2 mol%. The decrease of this lower transition temperature was assumed to be closely related with the secondary phase formation when Nb concentration greater than 1.2 mol%. From XRD analyses, a large amount of secondary phases was observed when Nb2O5 amount exceeded 1.2 mol%. The coefficients of thermal expansion of Nb-doped BaTiO3 were increased with increasing Nb2O5 contents, resulting in large internal stress between cores and shells. Therefore, the shift of Curie temperature to higher temperatures was attributed to internal stress resulting from the formation of a core-shell structure and a large amount of secondary phase grains.