CaCO3 was crystallized from CaCl2 solution containing commercially available 1-hydroxyethylidene-1,1-diphosphonic acid, Aqua soft having a chelating value of 330 (AS 330). The effect of the concentration of AS 330 and the temperature of crystallization on the morphology and crystalline structure of CaCO3 was investigated. The samples were characterized using scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The presence of AS 330 favored ternary calcite-vaterite-aragonite mixture at 60 and 80 degrees C and a binary calcite-vaterite mixture at 100 degrees C. Rhomboidal calcite, needle/rod like aragonite and flower like vaterite were obtained under different conditions. In contradiction to the usual process of the transformation of amorphous CaCO3 into different polymorphic forms, the data confirmed calcite is the precursor for the flower structured vaterite. The mechanism of formation of the flower structured vaterite is discussed in detail. (C) 2012 Elsevier B.V. All rights reserved.