The present work deals with the preparation of mesoporous metal oxide systems by means of new block copolymer templates and the development of original structural characterization methods. In the first part of the work is shown that PIB-PEO block copolymers generate robust and highly porous metal oxide textures characterized by large pores of spherical form. Sol-gel mesoporous TiO2 films were also tested as semiconductors in dye sensitized solar cell devices noticing promising results in comparison with the nanoparticulate systems. Furthermore, the remarkable templating behavior of the PIB-PEO block copolymers is also presented by the preparation of hierarchical silica powders. Due to the structural complexity of these latter systems their characterization could not be exhaustively carried out by means of standard analysis approaches. The employment of the in-situ SAXS/SANS-physisorption technique provided thus an exclusive possibility to study in detail the porosity and its organization in these hierarchical materials. Interesting applications of this novel characterization technique are given also by the analysis of further systems like periodic mesoporous organosilicas (PMOs).