The crystallization of calcium carbonate was carried out by mixing CaCl 2 and Na 2 CO 3 solutions. The morphology of precursor formed prior to the nucleation of the polymorphous crystals (calcite and vaterite) varies depending on the feed concentration. The faster nucleation rate of polymorphous crystals in 0.2 mol/L than in 0.05 mol/L solution results in the prompt disappearance of the precursor at 0.2 mol/L. In 0.05 mol/L solutions the lifetime of the precursor is relatively long. The crystallization fraction of vaterite increases with the feed concentration and decreases with the addition rate of Na 2 CO 2 solution. Vaterite takes on the various morphologies of the aggregates of the primary flocculation body (spherulite) depending on the crystallization conditions. Vaterite transforms to calcite by a direct solution-mediated mechanism. During crystallization the concentration attains a stationary value, which increases with the feed concentration and decreases with the addition rate of Na 2 CO 2 solution. This may be due to the crystal size decrease expected from the Gibbs-Kelvin equation. Magnesium ion suppresses the transformation of vaterite by inhibiting the growth of the calcite. Magnesium ion is selectively included in calcite and causes the increase of the attained concentration and the remarkable change in the morphology of calcite especially in 0.05 mol/L solution.