Sulfonated polyether ether ketone (SPEEK)-based composite membranes doped with 23 and 50 wt% of hydrated tin oxide (SnO2·nH2O) were prepared and characterized for Direct Methanol Fuel Cell (DMFC) applications . The composite membranes were characterized in terms of ion exchange capacity (IEC), tensile tests, water uptake measurements, electrochemical impedance spectroscopy (EIS), and Pulsed-field-gradient spin-echo nuclear magnetic resonance (PFGSE NMR) spectroscopy. The body of results indicated the involvement of hydrated tin oxide in the proton conduction mechanism, the inorganic phase providing additional paths between the water clusters for proton transport. NMR measurements evidenced that SnO2·nH2O particles not only facilitate the proton transport but also hinder water diffusion. Therefore, due to the selectivity of SnO2·nH2O for proton diffusion, the filler effect was found to be also beneficial for the reduction of methanol crossover through the SPEEK membrane and for improving the performance of the SPEEK membrane when used as electrolyte in a DMFC test station.