Nano-engineered membranes obtained by electro-hydrodynamic technologies have been proposed as a good candidate for active filtration. The present work reports some results on the development, production and characterization of three different nanostructured membranes based on: electrospun TiO2 inorganic nanofibers, nanocomposite structures of polymer nanofibers with TiO2 embedded nanoparticles and multilayered structures of polymer nanofibers and electrosprayed TiO2 nanoparticles. Their catalytic activity on volatile organic compounds (VOCs) decomposition has been explored in a photoreactor properly design for this purpose and a comparison among their performance will be extensively discussed. Multilayered membranes showed a complete degradation of methanol in gas phase and the photo-catalytic activity has been found to be affected from the catalyst content and morphology, by means that there is a critical concentration of catalyst over which its increase results on worse photo-oxidation performance. Inorganic TiO2 based membranes revealed the same activity as the nanocomposite membranes, in terms of methanol reacted per gram of catalyst, but their poor mechanical properties makes them not suitable for a potential scale up. (C) 2013 Elsevier B.V. All rights reserved.