The influence of aliphatic organic additives including amines, diamines and amino acids, on the polymorph of calcium carbonate (CaCO3) precipitated from a calcium hydroxide (Ca(OH)(2)) suspensions and carbon dioxide gas (CO2) was studied by X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The amorphous calcium carbonate, vaterite, aragonite and calcite were observed for the precipitated samples with organic additives. While the precipitation without organic additive, only the stable phase; calcite was obtained. The observed crystal phases were related with the alkyl chain length in the aliphatic part of additives. These results suggested that hydrophobic interactions clue to the van der Waals force between organic additives and surface of inorganic precipitates could not be ignored. We concluded that covering or adsorbing of these organic additives on the precipitates surfaces retarded the successive dissolution/recrystallisation process in the aqueous systems. The results revealed that not only the polar interaction from the hydrophilic functional groups, as the former reports proposed, but also the van der Wools interactions from the hydrophobic alkyl groups played the important role in the phase transformation of CaCO3. (C) 2013 Elsevier B.V. All rights reserved.