Nanostructured TiO2 thin-film electrodes of controlled thickness were obtained by immobilization of TiO2 powder (Degussa P25) on SnO2:F (FTO)-coated glasses by electrophoresis. The photocurrent-potential characteristics of the electrodes in contact with an indifferent aqueous electrolyte, for both front- and backside UV illumination, show the existence of a macroscopic electric field in the electrode region near the FTO substrate. This electric field, which is only photoinduced in the presence of water (it does not appear in TiO2 dye-sensitized solar cells under visible illumination), apparently disappears when an efficient hole scavenger, like methanol, is added to the aqueous electrolyte. It is attributed to a nonhomogeneous spatial accumulation of photogenerated holes at surface-bound OH radicals resulting from the photooxidation of chemisorbed water molecules. The influence of film thickness and UV illumination mode (front- and backside) on the photoinduced electric field is analyzed by solving the transport equations for diffusion and drift of electrons.