Nanocrystalline TiO2 (anatase) films were prepared using either colloidal suspensions or a sol-gel route. The electronic structure of these films was analyzed using X-ray photoelectron spectroscopy, (XPS) and ultraviolet photoelectron spectroscopy (UPS). Apart from pristine films, films containing defects introduced by annealing under ultra-high vacuum conditions or by ion bombardment were investigated. Generally, annealing in the temperature range up to 720 K results in no significant changes in the XPS and LIPS spectra as compared to the pristine state, indicating that the amount of defect formation is too low to be observable by these techniques. On the other hand, ion irradiation causes the appearance of distinct defect states; these could be identified in agreement with previous data from photoemission studies on rutile and anatase single crystals. From UPS, a valence-band width of similar to 4.6 eV was determined for the nanocrystalline anatase films. (c) 2005 Published by Elsevier B.V.