A multilayer polyelectrolyte membrane for fuel cell applications includes a first perfluorocyclobutyl-containing layer that includes a polymer having perfluorocyclobutyl moieties. The first layer is characteristically planar having a first major side and a second major side over which additional layers are disposed. The membrane also includes a first PFSA layer disposed over the first major side of the first layer and a second PFSA layer disposed over the second major side of the first layer.