Nanostructured materials play a fundamental role in orthopedic research owing to their outstanding properties and excellent biocompatibility. Titania nanotube (TNT) arrays engineered by electrochemical anodization process have been extensively explored and used as effective carriers for controlled drug delivery. In this study, we proposed a drug delivery system based on coordination bond. Iron (III), Fe3+, on the nanotube surface can effectively bind to alendronate sodium (NaAL), a drug for the treatment of osteoporosis, through coordination bonds, which can be formed or broken through the change of pH, and thus can be controlled by pH. The pH-responsive system was prepared by three-step procedure: (i) fabrication of TNTs by electrochemical anodization, (ii) modification of amino groups on the surface of nanotubes by hydrothermal method, and (iii) amino-functionalized nanotubes by Fe3+ solution soak. The Fe-modified TNTs not only allowed alendronate-loading content of up to 50.2% by weight, which is significantly higher than most drug delivery systems previously reported, but also delayed and prolonged drug release. Moreover, in vitro drug release experiments demonstrated that coordination bond-based TNT system may have great potential applications in clinical use.