We have investigated new poly-vinylidene fluoride/poly-acrylonitrile (PVdF/PAN) based proton conducting membranes by means of vibrational spectroscopy. We find that a complete phase inversion occurs during the preparation procedure, when the gelling solvents are replaced by an acidic solution, providing the proton conducting property. The uptake of acid is promoted both by the presence of PAN and the ceramic filler, Al2O3. No particular interaction between the polymer matrix and the acidic solution could be detected, supporting the picture of an inert matrix entrapping a liquid component. However, the dissociation degree of the acid is decreased due to the spatial confinement in the membrane. By comparing the dissociation degree and the actual amount of acid in the membrane to the conductivity, we conclude that the limiting factor for the conductivity is the long-range mobility of the protons, which is governed by the morphology of the membrane. (c) 2005 Elsevier Ltd. All rights reserved.