Abstract: A process for preparing multi-layer proton exchange membranes (“PEM's”), and membrane electrode assemblies (“MEA's”) that includes the PEM. The process includes (a) providing an article that includes an ionomer membrane adhered to a substrate, the membrane having a surface available for coating; (b) applying a dispersion or solution (e.g., an ionomer dispersion or solution) to the membrane surface; (c) drying the dispersion or solution to form a multi-layer PEM adhered to the substrate; and (d) removing the multi-layer PEM from the substrate. Also featured a multi-layer PEM's and MEA's incorporating such PEM's.