High-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM) have been carried out on Si-doped sintered α-Al2O3. HRTEM shows that there is no amorphous phase at grain boundaries. The Si-segregated boundary is found to be much more sensitive to irradiation damage than undoped Al2O3 grain boundaries. AEM with energy dispersive x-ray spectroscopy (EDS) shows the significant segregation of Si at grain boundaries, and AEM with electron energy-loss spectroscopy (EELS) reveals the existence of six-fold coordinated Si at the grain boundaries. The theoretical calculations obtained by the molecular orbital method support the data obtained by EELS. © 1998 American Institute of Physics.