Titanium dioxide films were anodically formed at various potentials up to 65 V in 1M H2SO4. Oxide films were characterized by performing various techniques, including electrochemical impedance spectroscopy, scanning electron microscopy, Raman spectroscopy, ellipsometry and diffuse reflectance FT-IR spectroscopy. Low voltage anodization (up to 10V) results to amorphous TiO2, whereas at higher applied potentials (up to 65 V), anatase is the predominant form. Anatase films were further hydroxylated with an acidic agent and the effect of this treatment on the overall impedance of the electrodes was studied with impedance spectroscopy. The potential use of anodic (anatase) Ti/TiO2 electrodes in the development of impedimetric immunosensors is also demonstrated by monitoring the immunoreaction of avidin/anti-avidin with different instrumental approaches based on a FRA analyzer, an LCR-meter and a home-built charge integrator (Multipulser). (c) 2005 Elsevier Ltd. All rights reserved.