The influence of different water-soluble polysaccharides, dextrans (cationic, anionic and non-ionic) and soluble starch, on the precipitation of calcium carbonate, has been investigated in the model system in which calcium hydroxide and carbonic acid were reactants. In the absence of additives, the formation of metastable phases, vaterite and amorphous calcium carbonate is observed at the early stage of the process, and as a consequence of the solution-mediated transformation process calcite appears in the system as the only solid phase in equilibrium. In the presence of starch, vaterite is found in the final precipitate, with the content increasing with the increase of starch concentration, probably as a consequence of calcite nucleation and crystal growth inhibition. Non-ionic dextran causes the inhibition of vaterite nucleation, which results in the formation of calcite as a predominant solid phase throughout the precipitation process. The crystal size of the so-formed calcite reduces by increasing the relative molecular mass (M-r) of neutral dextran. The presence of charged dextrans, either cationic or anionic, causes inhibition of the overall precipitation process: in the case of anionic dextran the inhibition seems to be the consequence of its reaction with Ca2+ ions (supersaturation decrease), while cationic dextran most probably adsorbs electrostatically onto the negatively charged surfaces of calcite and vaterite. (c) 2008 Elsevier BY. All rights reserved.