With three kinds of plasma-sprayed hydroxyapatite coatings (HACs) prepared, the objectives of this study were (1) to establish the calibration methods for quantitatively measuring the concentration of impurity phases and the degree of crystallinity of the HACs, and (2) to explore the effects of postheat treatments at various temperatures in vacuo on the changes of phases and crystallinity of the HACs. By the internal standard method used, the concentrations of im- purity phases, such as a-TCP, p-TCP, and TP, of the assprayed HACs were significantly higher than those measured by the direct intensity-ratio method, and the CaO phase was lower than the direct intensity-ratio method. When the HACs were heat treated in the temperature in-terval 63&850ยฐC, the concentrations of impurity phases obviously decreased, and the coating crystallinity apparently increased. After annealing at 850"C, an HAC consisting of at least 95% crystallinity with few impurity phases was obtained. As the annealing temperatures in the interval 850-1000ยฐC were applied, however, the HA phase seriously decomposed, resulting in the appearance of a large number (higher than 20 wt%) of impurity phases in the HACs. This work suggests that the optimum heat treatment conditions in vucuo for maximizing crystallinity and minimizing impurity phases of the HACs do not occur at the same temperature.