In this work, highly conductive hybrid organic inorganic membranes loaded with SiO2, TiO2-P2O5 and SiO2-TiO2-P2O5 meso/macroporous particles were prepared via a sol gel process. Meso/macroporous particles were incorporated to hybrid membranes, for improving water retention and enhancing electrochemical performance. These particles with a polymodal pore size distribution were prepared by templating in highly concentrated emulsions, the particles showed a specific surface area between 50 m(2)/g (TiO2-P2O5) and 300 m(2)/g (SiO2-TiO2-P2O5). The particles were dispersed in a hybrid silica sol and further sprayed onto glass paper. The films were polymerized and sintered; those loaded with meso/macroporous particles had a homogenous distribution. High temperature proton conductivity measurements confirmed a high water retention. Conductivity of these materials is higher than that of Nafion (R) at higher temperatures (120 degrees C) (2.10(-2) S/cm). This study provides processing guideline to achieve hybrid electrolytes for efficient conduction of protons due to their high surface area and porous structure. (C) 2014 Elsevier B.V. All rights reserved.