The influence of the preparation method on the structure, conduction and photoelectrochemical properties of monomeric and polymeric tetraruthenated porphyrin films on ITO glass and nanocrystalline TiO2 has been investigated. The films were characterized by STM, MAC mode SFM, cyclic voltammetry, electrochemical impedance spectroscopy ( EIS) and combined electro-/photoelectrochemical techniques. The electronic diffusion coefficient DeCm2 of the films differed by three to four orders of magnitude depending on the procedure employed for the deposition process. The photoelectrochemical properties were evaluated either: by depositing the films directly on transparent ITO electrodes, under an applied bias potential and presence of O-2 as electron acceptor; or by depositing the porphyrin material on nanocrystalline TiO2 in a Gratzel-type cell. In the first case the porphyrin films exhibited a typical p-type semiconductor behavior described by a Schottky junction model, while in the second the films behaved as a sensitizer of an n-type semiconductor. The photoelectrochemical properties of the porphyrin films and their performance as sensitizer in Gratzel-type cells were found to be strongly dependent on the conductivity and packing characteristics of the material. Semi-empirical calculations were performed by modified MM2 and ZINDO/S methods, in order to simulate the packing and electronic structures of the tetraruthenated porphyrin.o TEXTO COMPLETO DESTE ARTIGO, ESTARÁ DISPONÍVEL À PARTIR DE AGOSTO DE 2015.44359366