In the present work, the influence of Cr and Ca co-additives on the phase formation under conditions emulated the real sintering process of Cr4+:YAG ceramics is studied. The XRD analysis of the treated samples revealed the difference in formation rates of intermediate phases between the samples with and without the Cr2O3 additive. The formation of intermediate phases in the solid-state reaction between Y2O3 and Al2O3 is observed to shift toward higher temperatures (ie, toward the stage of fast shrinkage) if the mixture of Cr2O3 and CaO is added. The reason for such shift is the appearance of new intermediate, which contains Cr4+ ions in perovskite structure, as has been established by optical absorption and luminescent investigations. It is found that the Cr,Ca:YAG ceramics prepared by vacuum solid state reaction sintering at 1750 degrees C, 10hours possesses better optical transparency than Ca:YAG ceramics prepared under the same conditions.