The present invention relates to a reference electrode for a potentiometric electrode system, characterized in that the junction in contact with a sample solution is enlarged and an ion-sensitive membrane containing an ion selective material as a protective membrane for the inner reference solution is employed, which comprises a substrate; a metal layer; an insoluble metal salt layer; an insulating film for insulating the metal layer from an aqueous solution; a hydrogel serving as an inner reference solution; the junction on the hydrogel contacting with a sample solution; the ion-sensitive, protective membrane formed over all surface areas of the hydrogel, except for the junction, to separate the sample solution from the inner reference solution or act as an ion-sensing membrane upon the contamination of the junction, whereby the operational abnormality caused by junction contamination may be easily checked and fast activation may be achieved.