Microstructured biomaterials such as nacreous layer from mollusk shells receive much attention at present. The progress in studies on the microstructure, orientation of aragonite crystal in nacreous layer, and the biomineralization formation theory of nacreous layer were reviewed in this article. Additionally, the inspiration of the particular principles and mechanisms of self-assembly in nacreous layer for fabrication of biomimetic materials were also discussed. It's believed that choosing the appropriate organic substances, and self-assembly into supramolecular structures as the templates for the depositing of inorganic materials, are crucial for biomimetic synthesis.