The method for the production of multilayers comprises: applying a coating solution (I) which comprises a dissolved or dispersed proton-conductive polymer and a solvent (Is) containing water in amounts from 25 to 60 wt % and an organic solvent in amounts from 75 down to 40 wt %, on an electrode, applying a coating solution (II) which comprises a dissolved or dispersed proton-conductive polymer and a solvent (IIs) containing water in amounts from 0 to less than 25 wt % and an organic solvent in amounts above 75 wt %, on the wet first coating without any drying of the first coating; and drying the coatings to form an electrolyte membrane. The methods can provide multilayers capable of satisfactory power generation properties as an electrode structure by forming an electrolyte membrane on an electrode without causing any penetration of electrolyte into the electrode.