Recently, interest in electrochemical formation of hydroxyapatite has evolved. In this work, highly crystalline hydroxyapatite is electrodeposited on pure titanium and Ti-6Al-4V alloy. In situ and ex situ imaging, coupled with potentiostatic and potentiodynamic measurements, is conducted by means of electrochemical atomic force microscopy. This allows for a study of the nucleation and growth of hydroxyapatite as well as of its near-atomic structure. Electrodeposition of hydroxyapatite is shown to result from precipitation in solution, following two stages: (1) instantaneous nucleation, two-dimensional growth; (2) progressive nucleation, three-dimensional growth. Although some nucleation occurs already at -842 mV, potentials that are more negative than -1.26 V versus SCE are required for enhanced growth. Mass transport is found to have only secondary effect on the deposition process. The conclusions of this work have implications in optimization of coatings on implants as well as in enhancement of the understanding of bone mineralization in vivo.