Titanium (Ti) and its alloys have been applied in orthopedics as one of the most popular biomedical metallic implant materials. In this work, to enhance the bioactivity, the surface of Ti alloy pre-modified by silane coupling agent and glutaraldehyde was covalently grafted with chitosan (CS) via biochemical multistep self-assembled method. Then, for the first time, the achieved surface was further immobilized with casein phosphopeptides (CPP), which are one group of bioactive peptides released from caseins in the digestive tract and can facilitate the calcium adsorption and usage, to form CS-CPP biocomposite coatings. The structure and composition of the fabricated coatings were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and atomic force microscopy (AFM). As the experimental results indicated, multi-step assembly was successfully performed, and the CS and CPP were assembled onto the Ti alloy surface orderly. It is anticipated that the Ti alloys modified by CS-CPP biocomposite coatings will find potential applications as implant materials in biomedical fields.