Three kinds of chemical processes, citrate gel process, acetate gel process, and coprecipitation route, have been applied to the synthesis of homogeneous metastable tetragonal (t′) and cubic solid solutions of ZrO2−X mol% CaO (X = 4–20). From a Raman scattering study, the citrate gel process based on the gelation of the aqueous solution of citric acid containing Zr and Ca ions was found to produce compositionally homogeneous samples in comparison with the other two methods. The axial ratio c/a decreases with increasing concentration of CaO and becomes unity around 8–10 mol% CaO composition.