Non-natural mineralization of CaCO3 with special structures or morphology is generated during the crude oil migration, which is the main scale of alkaline/surfactant/polymer (ASP) flooding in oilfields, adversely affecting the oil recovery and causing environmental pollution. Up to now, the mineralization of superstructural symbiotic aragonites and the role of heavy alkyl-benzene sulfonate (HABS) in directing mineralization are still unclear. In this work, rosette-like, bouquet-like and dumbbell-like aragonite-based superstructure of symbiotic CaCO3 crystals were obtained in a simulated O/W emulsion with HABS, which can help understanding the diversified growth of CaCO3 scaling in oilfield. As a result, HABS stabilized micelles acted as a framework for mineralization, and promoted the accumulation of Ca2+ and CO32-, generating pre-nucleation clusters and partial ion pairs by electrostatic attraction. Following, the sequential nucleation of amorphous CaCO3 interconnected with HABS molecules. Finally, these nanoparticles transformed into micro-meter crystals via dissolution-reprecipitation, forming the superstructures that controlled by a synergistic effect between HABS and kerosene phase. This work may enrich the understanding of CaCO3 mineralization in oilfield, provide theoretical support for the prevention of hard carbonate scaling, and also provide a novel strategy for organic-inorganic composites manufacturing.