This study aimed to improve osteointegration performance of the new innocuous Ti–18Zr–13Mo implant through constructing hierarchically structured bioactive coating. A micro/nano-scaled fibrous network topography as well as bioactive components of calcium phosphate compounds were assigned to Ti–18Zr–13Mo alloy surface by a two stepped hydrothermal process for making its physical structure and chemical composition more closer to natural bone tissue. Scanning electron microscopy, transmission electron microscope, energy dispersive spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy and contact angle measurement had been applied to characterize the surface coating. Furthermore, we in-depth explored the formation process and mechanism of the hybrid bionic coating using knowledge of energetic and crystallography. Following the treatment, the coated Ti–18Zr–13Mo implant showed significant boosting of MC3T3-E1 osteoblasts’ activity, adhesion and differentiation ability in vitro. The modification technology of the hierarchical bioactive coating can provide a strong guarantee for practical orthopedic and dental applications of Ti–18Zr–13Mo implant. Besides, the promising results will further expand the research fertile ground of Ti-based alloy and other metal implant and prosthesis.Graphical abstract: