Multistructured membranes based on ultrafine fibers of polymethylmethacrylate-co-methacrylic acid (PMMA-co-MAA) and TiO2 nanoparticles have been obtained by electrohydrodynamic (EHD) technologies, for active filter media manufacturing. Process optimization of the nanofibers based layers has been investigated by response surface methodology (RSM) in order to predict the domain of the parameters where the smallest fiber diameter can be achieved. A quantitative relationship between electrospinning parameters and the responses (mean diameter and standard deviation) was established and then the final multi-layers structure of nanofibers and nanoparticles has been achieved for a controlled and robust process. The nanostructured membranes have been characterized by SEM imaging, EDAX, TGA analysis and water vapour permeability and their photocatalytic activity has been tested on VOCs degradation. (C) 2011 Elsevier Ltd. All rights reserved.