Recently there is increasing evidence that the shell biomineralization proceeds via an amorphous precursor route. Therefore, the search for and investigation of amorphous biominerals in bivalve shells are of great importance and interest. Here, using a scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), and Fourier transform infrared spectrometer (FTIR), we investigate the microstructure and mineralogy of the periostracum in Perna viridis. We find that: (1) the periostracum has three layers, of which the inner and outer layer are of proteins, while the middle layer is mineralized with nanospheres of amorphous biominerals; (2) the nanospheres are of amorphous carbonated Ca-Mg phosphate (ACCP), where the CO32-/PO34- weight ratio is estimated to be similar to 0.3, and the Ca/P and Ca/Mg atomic ratio is similar to 1.4 and 1.6, respectively; (3) the nanospheres, with a diameter of 43106 nm, are found to assemble into spherules with a diameter of 160-500 nm, which are further organized into parallel microlayers separated by the proteins; and (4) the nanospheres are assumed to function as the pH stabilizer to facilitate the shell's initial mineralization. Finally, we expect that these findings will advance our understanding of the shell's biomineralization process. (C) 2014 Elsevier Inc. All rights reserved.