Precipitation of hydroxyapatite on titanium from aqueous solution offers the possibility of creating biologically active coatings for bone fixated implants by mimicking the physiological properties of the bone. While solution-related factors have been well established, the research into surface-related stimuli for promoting hydroxyapatite nucleation is still underway. In the present work titanium surfaces were pretreated by implantation of sodium ions yielding sodium titanate incorporated within the surface layer with concentration, depth distribution, and morphology depending on the parameters of the ion implantation and the subsequent thermal treatment. Such ion-implanted surfaces were observed to promote hydroxyapatite nucleation and growth from simulated body fluid. Surface properties were studied using spectroscopic and microscopic methods. The mechanisms of heterogeneous nucleation of hydroxyapatite were discussed in terms of the electrical double layer.