The biomimetic structure and composition of biomaterials are recognized as critical factors that determine their biological performance. A bioinspired nano-micro structured octacalcium phosphate (OCP)/silk fibroin (SF) composite coating on titanium was achieved through a mild electrochemically-induced deposition method. Findings indicate that SF plays a critical role in constructing the unique biomimetic hierarchical structure of OCP/SF composite coating layers. In vitro cell culture tests demonstrate that the presence of OCP/SF composite coatings, with highly ordered and hierarchically porous structure, greatly enhance cellular responses. The coatings developed in this study have considerable potential for various hard tissue engineering and applications.