Proteins play important roles in the process of biomineralization. Vaterite and calcite have been synthesized by the reaction of Na2CO3 and CaCl2 in the bovine serum albumin (BSA) and agar system. The samples have been characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The shape of CaCO3 crystal has been analyzed by scanning electronic microscopy (SEM). The results show that calcite is a single product in the absence of BSA, but the product is a mixture of calcite and vaterite in the presence of BSA. The spheral shell of CaCO3 crystal was obtained when the concentration of BSA increased to 9.0 mg/mL.