Hollow hydroxyapatite (HAP) microspheres with pores on their surfaces were prepared by converting Li(2)O-CaO-B(2)O(3) (LCB) glass microspheres in phosphate solution. The structure, phase composition, surface morphology, and porosity of the hollow HAP microspheres were characterized by SEM, SEM-EDS, XRD, FTIR, ICP-AES, and N(2) adsorption-desorption techniques. The formation and conversion mechanism of the hollow HAP microspheres during immersion process were discussed. The as-prepared microspheres consisted of calcium deficient carbonated hydroxyapatite, which is biomimetic. FTIR spectra indicated that the resulting apatite were B-type CO(3)HAP, in which carbonate ions occupied the phosphate sites. After 600 degrees C heating treatment, hollow microspheres were completely composed of calcium deficient hydroxyapatite crystals including CO(3)(2-). The pore size distribution of the as-prepared hollow HAP microspheres were mainly the mesopores in the range of 2-40 nm with the pore volume 0.5614 cm(3)/g, and the mean pore size 10.5 nm, respectively. The results confirmed that LCB glass were transformed to hydroxyapatite without changing the external shape and dimension of the original glass object and the resulting microspheres possessed good hollow structures. Once immersed in phosphate solution, Ca-P-OH hydrates were in situ formed on the surface of the glass and precipitated in the position occupied by Ca(2+), while the pores were formed in the position occupied by Li(+) and B(3+). These hollow HAP microspheres with such structures may be used as promising drug delivery devices. (C) 2011 Elsevier B.V. All rights reserved.