Multi-layer polyelectrolyte membranes are described wherein at least one of the layers contains at least one acrylic resin or vinyl resin having at least one ionic or ionizable group, and at least one additional polymer. The polymer has small or large domain sizes with respect to he acrylic resin or vinyl resin that is present in one or more layers. The polymer preferably has improved conductivity when formed formed into a film. The membranes are useful in batteries, fuel cells, and the like.