In this paper, using sodium phosphate and calcium nitrate as reagents, nano-hydroxyapatite (n-HA) was synthesised under 8 conditions. The morphology and crystallinity of these prepared HA were investigated by Transmission Electron Microscope (TEM) and X-ray diffraction pattern (XRD). The Ca/P molar ratio of n-HA was tested by chemical method. In order to find a better way to obtain purer nano-hydroxyapatite, the phases transition and purification of these 8 samples before and after sintering at 1000°C were compared. The results indicated that all these samples showed similar, poorly crystallized apatite structures before sintering. The adding order between calcium and phosphate would affect the crystallinity, structure and Ca/P molar ratio of hydoxyapatite significantly. XRD analysis showed that adding sodium phosphate into calcium nitrate could gain more HA phase after sintering at 1000°C. The pH of reaction system had obvious effects on the structure of hydroxyapatite. Besides the pH of reactants also affected the structure of hydoxyapatite.