Hydroxyapatite has been synthesised via ball-milling precipitation method with calcium hydroxide (Ca(OH)2) and phosphoric acid (H3PO4) as precursors. The reaction products are ball-milled to accelerate the synthetic process. The finally obtained powders were characterised by X-ray diffraction, transmission electronic microscopy and scanning electronic microscopy. The results show that in the X-ray diffraction pattern of hydroxyapatite powders synthesised via ball-milling, β-TCP and CaO peak disappear, the crystallinity of hydroxyapatite powders increases, the size distribution of hydroxyapatite powders is narrower and aggregation of powders is obviously improved. This work suggests that ball-milling process advances the degree of reaction of Ca(OH)2–H3PO4 system, improves the purity and crystallinity of hydroxyapatite powders, decreases hydroxyapatite particles size, narrows the distribution of particles size and effectively reduces powders’ aggregation without adding any dispersing agent.