A new biomimetic process for apatite coating on polymeric materials has been developed. In this process, the surface of a polymer is modified with amorphous calcium phosphate (ACP), and then the polymer is immersed in a supersaturated calcium phosphate solution. The new biomimetic process has the advantages of safety, simplicity, and applicability to various types and forms of polymeric materials. By adding a biomolecule (such as protein, antibacterial agent, or DNA) to the supersaturated solution, immobilization of a biomolecule into the apatite coating while retaining the intrinsic biological activity of the biomolecule is possible. As a result of this, the base polymer would possess biological activity to control cell behaviors (such as adhesion, proliferation, and differentiation), in addition to good biocompatibility owing to the apatite. Hence, the new biomimetic process and the resulting composites have a wide variety of biomedical applications including tissue engineering scaffolds, percutaneous devices, and gene delivery carriers.