Abstract The standard molar Gibbs free energy of formation of CaCr 2O 4 from CaO and Cr 2O 3 has been determined by the e.m.f. measurement of galvanic cells involving a single crystal CaF 2 and a polycrystalline CaZrO 3 solid-state electrolytes in the temperature range (1073 to 1273) K. Reproducible e.m.f. values were obtained. The average values of the standard molar enthalpy and the standard molar entropy in the temperature range covered by the e.m.f. measurements have been also estimated. The results have been compared with those obtained by other authors.