We present flexible nacre-like multi-layered films of chitosan and hydroxyapatite using manipulation of inherited polymeric phase separation in the solidification process. Films were characterized as homogeneous dispersity, high mechanical strength, and ordered microstructure in given optimized conditions of temperature and composite ratio. It resulted that the initial solidification temperature and the composition ratio are important factors in determination of homogeneity and mechanical strength of organic/inorganic composites. These films might be suitable for further osteological applications with surgical appliances, wound dressings, and space-filling implants.