Local electronic excitations of Nb-doped BaTiO3 electroceramic were investigated using low-loss electron energy loss (EEL) spectroscopy with a transmission electron microscope. The variations in electronic structure of the BaTiO3 were monitored as a function of Nb content by using Kramers-Kronig analysis of the low-loss EEL spectra. We found that the valence state of Nb (+5) as compared with that of the Ti (+4) introduces changes in the valence and conduction band states of BaTi1-xNbxO3 samples. The real part of the dielectric function, Re(1/epsilon), displays an increasingly less negative char. acter with higher amounts of dopant and the valence plasmon exhibits "quasi-plasmon" characteristics with the addition of Nb (at 0.0-1.8 at.%). Further, the plasmon energy shifts (by about 0.5 eV) to higher values with Nb additions. Significant changes take place in oscillator strengths of excitations in local (nanometer-scale) regions of the perovskite samples. This investigation demonstrates a method to quantitatively assess electronic properties, at the submicrometer scale, of doped ceramics used in electronic and electrooptical applications.