A solid state Hg(Au)/HgO reference electrode was prepared utilizing gold amalgam solid particles. Solid fine powder of the gold amalgam was prepared by chemical reduction of Au(III) with NaBH4 followed by reduction of Hg(II) in the presence of gold fine particles. The solid content in the suspension of the gold amalgam particles and fine mercury oxide particles in DMF containing PVC was precipitated by the addition of a large amount of water to give solid Hg(Au)/HgO/PVC mixture. After drying, the mixture was pressure-molded to a physically stable Hg(Au)/HgO composite reference electrode material. The electrochemical characteristics of the electrode as a reference electrode were very similar to an ordinary Hg/HgO reference electrode. The electrode material can be molded and fabricated in any desired shape and size. The surface can be renewed by a simple polishing process whenever contaminated or deactivated. The applicability of the electrode in the electrochemical detection of carbohydrates after anion exchange separation was evaluated.