Sulfonated polyetheretherketone (sPEEK) membranes have been developed in which a hierarchical organisation into multilayers has been favoured during preparation using solvent casting. Bilayer membranes comprising sPEEK of different degrees of sulfonation (having ion exchange capacities between 1.1 and 1.6 meq g(-1)) have been characterised for their water uptake properties and proton conductivity. The composite membranes show no tendency to delaminate, even under prolonged operation in a hydrogen - oxygen fuel cell. By associating sPEEK of different water uptake characteristics, water back diffusion in an operating fuel cell is favoured, leading to a degree of control over the direction of water production at the anode or the cathode. Such a bilayer membrane has been operated at 110 degrees C without reactant gas hydration for over 900 h.