Nanostructured palladium thin films have been photochemically obtained by direct UV irradiation (254 nm) of a Pd[C8H17COCHCOC4H 9]2 amorphous film deposited on Si(100) and on ITO glass by means of the spin-coating technique. The UV photolysis of thin films of palladium b-diketonate complex results in the loss of all ligands from the coordination sphere. The acetylacetone derivative was chosen for its solid photochemistry, because the presence of branched hydrocarbons substituents lowers the intermolecular interactions, and allows the formation of high quality films upon spin-coating. The product of this photolysis was analyzed by XRD, SEM, and microanalysis. Afterwards, the film photodeposited on ITO glass was electrochemically studied, applying successive triangular scannings in a potential range of 0.00-1.30 V vs SCE for 15 minutes, in an electrolytic solution consisting in H2SO4 0.50 M. The modified electrode showed a profile similar to that of a palladium foil, although it is possible to observe that the peak potential shifts in 0.04 V approximately towards less positive values for the modified system, which is indicative of a possible catalytic effect. Based on these data, the modified ITO/Pd system was tested as an electrodic substrate for aniline polymerization in 0.10 M H2SO4; there obtaining a polymeric deposit, at lower potentials than those required when palladium foil was used as electrode, thus indicating that the method described may constitute a very interesting tool for the preparation of modified electrodes which may be advantageously used in the preparation of polymeric materials