Ni/YSZ ($Y_2O_3$-stabilized $ZrO_2$) composite powder for a cathode material in high temperature electrolysis(HTE) was synthesized by a mechanical alloying method with Ni and YSZ powder. Microstructure of the composite and cell thickness for HTE reaction has been analyzed with various techniques of XRD, SEM to investigate effects of fabrication conditions. Employing the composite material, furthermore, the unit cell for HTE has been studied to evolve hydrogen from water. XRD patterns showed that the composites after wet mechanical alloying were composed of respective nano-sized crystalline Ni and YSZ. While ethanol as additive for mechanical alloying increased to $20;{mu}m$ of average particle size of the composites, alpha-terpineol effectively decreased to sub-micro size of that. This study has been found out the evolution of hydrogen by HTE reaction employing the fabricated cathode material, showing 1.4 ml/min of $H_2$ generation rate as increasing $20;{mu}m$ of cathode thickness.