Hydroxyapatite (HA) powder suspension in deionized water was used as a dielectric liquid during electrical discharge machining (EDM) of Ti6Al4V work material. The machined surfaces were evaluated by scanning electron microscopy (SEM), energy dispersive spectroscopy, and optical microscopy. The powder particles in the dielectric liquid extensively migrated and formed an HA-rich layer on the work material surface under specific machining conditions. The result was attributed to the generation of secondary discharges due to altered discharge conditions. The particles divided the primary discharge channel into several secondary ones. When the main discharge channel subdivided into several sub-discharges with comparable energy densities, the particles in the discharge region got stuck among them. Then, they moved toward the melted cavities and penetrated the surface at the end of the discharge duration. The results suggest the process as a practical alternative for producing biocompatible interfaces or coatings for medical applications.