Pulsed laser ablation in liquid medium was successfully employed to synthesize hydroxyapatite colloidal nanoparticles. The crystalline phase, particle morphology, size distribution and microstructure of the hydroxyapatite nanoparticles were investigated in detail. The obtained hydroxyapatite nanoparticles had spherical shape with sizes ranging from 5 to 20 nm. The laser ablation and the nanoparticle forming process were discussed with explosive ejection mechanism by investigating change of surface morphology on target. The analytical results of XPS, FT-IR and Raman spectroscopy confirms that the stoichiometry and bonding properties of the hydroxyapatite nanoparticles are in good agreement with reported bulk hydroxyapatite materials.