Thermally processed hydroxyapatite coatings used on dental implants and hip prostheses for enhanced fixation may typically consist of a number of chemical and structural phases. These phases affect coating performance and tissue attachment. Hydroxyapatite was plasma sprayed to examine the phase evolution during processing. Coatings were examined with X-ray diffraction and elemental analysis. Results indicate that phase transformations are produced by (a) preferential removal of hydroxyl and phosphate leading to a change in melt composition, and (b) the high cooling rate due to the thermal spray process. Hydroxyl group removal promotes the amorphous phase and oxyapatite. Further heating produces a less viscous melt facilitating decomposition of hydroxyapatite to tricalcium and tetracalcium phosphate. Phosphate removal during flight produces a more calcium-rich melt preferring tetracalcium phosphate and calcium oxide formation. A proposed model shows the phase location within the lamellae of these coatings. Coating processes must thus prevent removal of hydroxide and phosphate during processing to maximize the hydroxyapatite content.