Inspired by mineralization in biological organisms, the production of higher ordered CaCO3 crystals modified by surfactants has received much attention. Normal micelles formed by anionic surfactant, sodium bis-2-ethylhexyl-sulfosuccinate (aerosol OT, ROT), was used as a template to direct the growth of CaCO3 crystals in the present work. When the concentration of the ACT increased from 0.5 to 5.0 mM, the polymorph of CaCO3 crystals changed from almost pure aragonite to almost pure vaterite at 150 degrees C. In the meantime, various morphologies of vaterite were obtained, such as astral and hexagonal structures. Based on the time-resolved experiments, we suggested that ACT micelles induced the formation of these structures. And the micelles were wrapped in the hexagonal structures, and dissolved in the aqueous solution with increase of the experimental time. Thus, hollow shells were produced. Abnormal polymorph transformation of CaCO3 crystals from the calcite to the vaterite was found. These effects of ACT on polymorph and morphology of CaCO3 crystals have not been reported as far as we know. (C) 2012 Elsevier Ltd. All rights reserved.