In this article, a specific system for both hydrogen formation and hydrogenation of compounds with hydrogen permeable membrane electrode by electrolysis of water is introduced. Hydrogen permeable palladium membrane played an important role as a cathode for electrolysis of water and hydrogen purifier by the permeation of hydrogen produced. The high pressure at electrolysis side improved a amount of hydrogen permeated through the membrane. The hydrogenation of organics proceeded in Pd surface and catalysts near the membrane. This system is compact and useful for production of hydrogen and chemical hydride in a narrow space.