The microstructure and composition of TiN films, formed by ion beam enhanced deposition (IBED) with different energy (40 keV and 90 keV) xenon ion bombardment and by simple physical vapor deposition (hereafter S-PVD) without any ion beam enhancement, and the interfaces between TiN films and Si substrates have been studied by cross-sectional view analytical electron microscopy in this work. Both the IBED TiN films prepared by Xe+ bombardment with either 40 keV or 90 keV energy ions and the S-PVD TiN film consist of nanocrystals. The TEM observations in the S-PVD case reveal an amorphous layer and a mixed layer of TiN grains and amorphous material at the TiN/Si interface. The thicknesses of the amorphous layer and the mixed layer are about 210 nm and at least 40 nm, respectively. Upon 40 keV Xe+ bombardment, an amorphous Si transition layer of about 50 nm thickness is found at the TiN/Si interface, and the TiN grains close to the TiN/Si interface are of weak preferred orientation. Upon 90 keV Xe+ bombardment, amorphous TiN and Si layers are found with a total thickness of 80 nm at the TiN/Si interface, and the TiN grains near the TiN/Si interface are of preferred orientation TiN ‖ Si. The energy of xenon ion bombardment has a strong effect on the microstructural characteristics of TiN films and the interfaces between the TiN films and the Si substrates, as well as the size and the preferred orientation of TiN grains.