Electrochemical impedance spectroscopy measurements of pulsed laser deposited single crystal anatase TiO2 thin films with various concentrations of Ta substituting for Ti were carried out. The qualities of the films were characterized by X-ray diffraction and Rutherford back scattering-channeling measurements. UV-visible measurements show a systematic increase of the bandgap with Ta incorporation. Corresponding Mott-Schottky plot was applied to obtain a continuous shift of the flat band potential with increasing free charge carrier (provided by Ta) concentration. This was verified theoretically by ab initio calculation which shows that extra Ta d-electrons occupy Ti t2g orbital with increasing Ta concentration, thereby pushing up the Fermi level. The Mott-Schottky results were consistent when compared with Hall effect and temperature dependent resistivity measurements. From the measured deviation of carrier densities from Hall and Mott-Schottky measurements we have estimated the static dielectric constant of the TiO 2 as a function of Ta incorporation, not possible from capacitive measurements. © 2011 Author(s).