Stoichiometric, and doped with a small amount of CaO, calcium zirconate dense samples were prepared. X-ray analysis revealed that the solid solution was formed in the concentration range up to x = 0.06 in the {xCaO + (1 - x)CaZrO3} mixture. The activity of CaO in the solid solution was determined by the emf method at the temperatures 1073 and 1273 K. The electrical conductivity was measured using both dc four-probe and ac impedance spectroscopy methods. The maximum conductivity values were observed for the sample with x = 0.06. This sample was used for further investigation. The oxygen-ion transference number, estimated by the emf method, appeared to be close to unity. The partial electronic (electron and electron hole) conductivities, deduced from current-potential curves following the polarisation method, were found to be very small with respect to total electrical conductivity. Then, the sample was tested as an electrolyte in solid oxide galvanic cells. In this way, the values of the standard free enthalpy of formation of cobalt and nickel silicates at the temperatures 1073 and 1273 K were determined and compared with those obtained by other authors.