Hollow hydroxyapatite (HAp) microspheres a few tens micrometers in diameter were fabricated by precipitating HAp preferentially on the surface of an organic polymer template using enzymatically supplied precipitant. The template, poly-divinylbenzene (PDVB) microsphere encapsulating urease, was synthesized in W/O/W emulsion. HAp was precipitated on the surface of the template as ammonia was enzymatically supplied from inside of the template in a solution containing calcium ion, phosphate ion and urea. Within 21.6 ks, the surface of the template was covered with HAp. After the template was removed by calcination at 873 K, the HAp hollow microspheres were obtained. The size of the HAp microspheres reflected that of the template and the latter was easily controlled in a range from 10 to 200 μ m by the preparation condition of the W/O/W emulsion. The shell thickness of the HAp sphere was also regulated by the duration of the enzymatic reaction. This material can be a promising candidate for the carrier of the drug delivery system.