Solid oxide fuel cells based on doped ceria electrolytes offer operating temperatures of ~600 °C. During recent years much atten- tion was aimed at successful powder preparation with high sinter activity and high conductivity. The properties of ceria electrolyte are very sensitive to impurities introduced during powder and electrolyte fabrication. One of the most successful and commercially available processes for the production of clean powders is based on the addition of several percent metallic cations that will react with impurities and segregate into the triple points of grain boundaries. In this work the results obtained from doping of CGO20 by 2% Ca and prepared by different routes were presented. The way of introducing Ca seemed to play an important role. During recent years much attention was aimed at successful powder preparation with high sinter activity and high conductivity. The properties of ceria electroly are very sensitive to particularly introduced during powder and electrolyte fabrication. One of the most successful and commercially available processes for the production of clean powders is based on the addition of several percent metallic cations that will react with impurity and segregate into the triple points of grain boundaries. results obtained from doping of CGO20 by 2% Ca and prepared by different routes were presented. The way of introducing Ca seemed to play an important role.