Understanding mechanisms in DSSCs is fundamental for their improvement; this includes the nanocrystalline semiconducting layer behaviour. Different mesoporous TiO2 layers are fabricated and analyzed for possible use in DSSC solar cells. The preparations included the addition of P123 triblock copolymer as structuring agent to the synthesized anatase sol. This preparation was also mixed with Degussa P25 TiO2 nanoparticles in one case and polystyrene latex in another. Mesoporous mixed TiO2-SiO2 thin layers were also analyzed. The diverse morphologies and features are studied by microscopic techniques and by means of spectral quantum efficiency of a photoelectrochemical cell (PEC) that uses as photoelectrode the unsensitized porous TiO2 layer. Contact angle measurements are also performed. We have found that a very high specific area due to very small nanocrystals and small pores can hinder electrolyte penetration in the pores formed by TiO2 nanograins, affecting photoelectrodes efficiency. © EDP Sciences, 2015.