The formation of vaterite is well known to be influenced by many low molecular weight additives. In this study, Density functional theory calculations was employed to study the effect of biological material lysine(Lys), aspartic acid(Asp), threonine(Thr) and glycine(Gly) on the formation of vaterite CaCO₃. The interaction energies between Gly and CaCO₃(110) and (104) surfaces were −2.618 and −1.784 eV, respectively. With the molar ratio of Ca²⁺ to Gly at 1.5, the reaction time of 11.5 min, the pH value of 7.5, the crystalline product of the reaction was almost monodisperse spherical vaterite in Ca(OH)₂-Gly-CO₂ reaction system. The obtained products were characterized by the XRD, RAM, SEM, TEM, and FT-IR. The results showed that the increase of Gly concentration inhibited the nucleation and the growth of calcite. Lys, Asp, Thr and Gly were employed as stabilizers for controlling particles, the crystalline product of the reaction was almost monodisperse vaterite CaCO₃. Its surface chemistry can be explored using this mechanism analysis. The methods are expected to be a reference for industrial production process.