In recent years extensive studies have been continuously undertaken on the design of bioactive and biomimetic dental implant surfaces due to the need for improvement of the implant-bone interface properties. In this paper, the titanium dental implant surface was modified by a bioactive vitamin D3 coating prepared by self-assembly process. Surface characterization of the modified implant was performed by field emission scanning electron microscopy (FE-SEM), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements (CA). Implant’s electrochemical stability during exposure to an artificial saliva solution was monitored in situ by electrochemical impedance spectroscopy (EIS). Experimental results obtained were corroborated by means of quantum chemical calculations at the density functional theory level (DFT). The formation mechanism of the coating onto the titanium implant surface was proposed. During a prolonged immersion period, the bioactive vitamin D3 coating effectively prevented the underlying titanium from corrosive attack (polarization resistance in order of 10⁷ Ω cm²) with ~95% protection effectiveness.