TiO2 films doped with 6% Fe were prepared by pulsed laser deposition (PLD) under different oxygen pressures, and characterized by X-ray absorption fine spectra (XAFS) and conversion electron Mossbauer spectra (CEMS). The edge energy and spectrum profiles of Fe- and Ti K X-ray absorption showed only Fe3+ and Ti4+ states for rutile TiO2 films prepared under 10(-1) Torr, the metallic Fe and Ti4+ for rutile TiO2 films prepared in 10(-6) Torr, and the metallic Fe and the average valance of less than "4+" for Ti in TinO2n-x films prepared by the PLD under 10(-8) Torr. The metallic Fe clusters are also found in the TEM images of TinO2n-x film. Magnetic property of Fe doped TiO2 films prepared by PLD at high vacuum (10(-6) and 10(-8) TorT) is considered to originate mainly from the magnetic metal iron clusters. (c) 2007 Elsevier B.V. All rights reserved.