A membrane-electrode assembly (MEA) 1 has a solid polymer electrolyte membrane 2. The membrane 2 has ion-conductive domains 3 and non-ion-conductive domains 4 and an electrode catalyst 5. The electrode catalyst 5 is present selectively on surface sites of the solid polymer electrolyte membrane 2 which corresponds to the ion-conductive domains 3 rather than surface sites of the membrane 2 which corresponds to the non-ion-conductive domains 4. A spray liquid containing the electrode catalyst and a solvent is applied onto a surface of the membrane 2 by electrostatic spray deposition to selectively adhere the electrode catalyst 5 on the surface sites of the membrane 2 which corresponds to the ion-conductive domains 3. The membrane 2 is preferably subjected to a hydrophilization treatment before being sprayed with the spray liquid.