In this paper, the crystallization behavior of calcium carbonate between the organic-water interfaces using a slow gas-diffusion procedure is studied. The organic-water interfaces can control the crystallization of calcium carbonate to form a flower-shaped superstructure. The precipitates of calcium carbonate were identified by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A possible mechanism about the self-assembly process of CaCO3 crystals has been analyzed. It is found that the morphology of CaCO3 superstructure depends on the properties of organic solvent. This paper also presents the influence of surfactant monolayer, between the biphase interfaces, on the CaCO3 superstructure. This study suggests that it is possible to control morphogenesis of calcium carbonate by a combination of a surfactant monolayer with the organic-water interfaces.