The synthesis of vaterite was attempted by carbonation process (Ca(OH)_2+CO_2→CaCO_3+H_2O) in aqueous systems with addition of organic compounds having amino group or carboxyl group such as amine, carboxylic acid salt and amino acid salt. Sodium L-glutamate, sodium L-aspartate and ethylenediamine are effective for crystallization of vaterite from amorphous calcium carbonate (ACC), as an initial product. ACC gradually crystallized to vaterite while releasing the additive and H_2O contained in ACC, under the absence of OH^- species in the liquid phase. The existence of OH^- in the liquid phase prevented strongly the formation of vaterite from ACC.