A simple method to prepare hollow hydroxyapatite (HAP) microspheres with mespores on the surfaces is performed using a precipitation method assisted with Li2O-CaO-B2O3(LCB) glass fabrication process. This research is concerned with the effect of sintering temperature on the microstructure evolution, phase purity, surface morphology, specific surface area, and porosity after sintering process. The microspheres were sintered in air atmosphere at temperatures ranging from 500 to 900 °C. The starting hollow HAP microspheres and the sintered specimens were characterized by scanning electron microscope, X-ray diffractometer, specific surface area analyzer, and Hg porosimetry, respectively. The as-prepared microspheres consisted of calcium deficient hydroxyapatite. The results showed that the as-prepared hollow HAP microspheres had the highest specific surface areas, and the biggest total pore volume. The pore size distribution of the as-prepared hollow HAP microspheres were mainly the mesopores in the range of 2～40 nm. The specific surface area and total pore volume of hollow HAP microspheres decreased with increasing sintering temperature. Whereas the mean pore size increased with increasing sintering temperature. It showed that at 700°C, Ca-dHAP decomposes into a biphasic mixture of HAP and β-calcium phosphate(TCP).