Vaterite has broad application prospects in the field of daily necessities and biomedical science because of its unique mechanical, physical and chemical properties. However, vaterite is the thermodynamically least stable phase in the three anhydrous crystalline phases of calcium carbonate, and such thermal metastability often transforms it into more stable aragonite or calcite phases, so how to inhibit the phase transformation of vaterite is always a hot topic in the study of calcium carbonate. In this paper, structure, properties, application, and phase transformation from vaterite to aragonite and/or calcite are briefly introduced. Particularly, based on the three basic routes of synthesis of calcium carbonate, some traditional methods, such as carbonization, double decomposition, microemulsion, solvothermal method, and some latest progress, e.g. self-assembly of monolayer, biomimetic synthesis and thermal decomposition methods of tuning and preparation on vaterite are then summarized. Moreover, some analysis on the mechanism of