The annealing behavior of a lanthanum oxide thin film deposited on a silicon (001) substrate by electron-beam evaporation has been studied by aberration-corrected transmission electron microscopy (TEM), scanning TEM (STEM), and electron energy loss spectroscopy (EELS). We have developed a procedure for the precise measurement of thickness and interfacial roughness by taking advantage of features of aberration correction combined with the statistics of fluctuating crystalline edge positions. The results of the measurements and quantitative elemental analyses by STEM-EELS have revealed atomic diffusion and reactions during deposition and postdeposition annealing (PDA) at 300 and 500 °C. The channel mobility could be limited by Coulomb scattering before PDA, and by remote roughness scattering and remote phonon scattering after PDA at 500 °C. When we consider the large leakage current caused by oxygen defects in the as-deposited sample and the large equivalent oxide thickness of the thick Si-rich layer in the 500 °C -PDA sample, the gate properties of the 300 °C -PDA sample should be better than those of other samples, as shown by electrical measurements.