Ethanol-calcium method was proposed, and the metastable vaterite phase of CaCO₃ was synthesized by this method, i.e. the complex compound between CaCl₂ and ethanol reacted with Na₂CO₃ aqueous solution. Effects of aging time and reaction temperature on the polymorphs and morphologies of CaCO₃ were investigated, and the comparative study on the synthesis of CaCO₃via ethanol-water binary solvent (EWBS) method at the same conditions was carried out. XRD results indicate that the fraction of vaterite in the product decreases with the aging time prolonging and reaction temperature increasing in both systems. However, the fraction of vaterite in the product prepared by ethanol-calcium method is much higher than that in the product prepared by EWBS method, and the stability of vaterite prepared by ethanol-calcium method is also much better. SEM observation shows that the morphologies of vaterite and calcite are their typical sphere and rhombohedra, respectively.