The effect of CuO as a sintering additive on the electrolyte of solid oxide electrolysis cells (SOECs) was investigated. 0.5 wt% CuO was added into Sc0.1Ce0.05Gd0.05Zr0.89O2 (SCGZ) electrolyte as a sintering additive. An electrolyte-supported cell (Pt/SCGZ/Pt) was fabricated. Phase formation, relative density, and electrical conductivity were investigated. The cells were sintered at 1373 K to 1673 K for 4 h. The CuO significantly affected the sinterability of SCGZ. The SCGZ with 0.5 wt% CuO achieved 95% relative density at 1573 K while the SCGZ without CuO could not be densified even at 1673 K. Phase transformation and impurity after CuO addition were not detected from XRD patterns. Electrochemical performance was evaluated at the operating temperature from 873 K to 1173 K under steam to hydrogen ratio at 70:30. Adding 0.5 wt% CuO insignificantly affected the electrochemical performance of the cell. Activation energy of conduction (Ea) was 72.34 kJ mol−1 and 74.93 kJ mol−1 for SCGZ and SCGZ with CuO, respectively.