Homogeneous CaCO3 microspheres were controllably synthesized via a simple hydrothermal method without using extraneous additives by Ca(OH)2 saturated solution reacted with CO2 storage material (CO2SM), which was obtained by absorbing CO2 gas in a system containing equimolar ethylenediamine (EDA) and polyethylene glycol 400 (PEG). Specifically, homogeneous pure vaterite spheres were obtained by using 160 g/L CO2SM solution at 100 °C and a reaction time of two hours. It is noteworthy that the EDA and PEG, which are released from CO2SM, have dual functions as a CO2 absorber and crystal regulator in the process of controlling the crystallization of CaCO3 crystals.