In this paper, calcium carbonate particles with unusual morphologies could be easily obtained by a precipitation reaction of sodium carbonate with calcium chloride from mixed solution of organic solvents and water in the presence of cetyltrimethylammonium bromide (CTAB) at 80 °C. The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The effects of different organic additives–glycol, glycerine, formaldehyde, acetaldehyde, glycol-methyl ether and glycol-ethylether, on the crystal form and morphology of the as-prepared CaCO 3 –were investigated and discussed. The results show that organic additives can have great influence on the forms and morphologies of CaCO 3 at relative high temperature in the presence of CTAB. Various unusual crystal morphologies, such as dendrite-shaped, flower-like, wheatgrass-like, needle-like, whiskers, double-taper-like, etc., can be obtained depending on the experimental conditions. In particular, pure aragonite with unusual morphologies can be produced in the presence of glycol, glycerine, glycol-methyl ether at 80 °C, respectively.