In this study, nano-hydroxyapatite (HA) powders were synthesized via a simple sol-gel method using Ca(NO3)2•4H2O and P2O5 as starting materials. Two different precursors, with and without citric acid (CA), were prepared. The transformation process of HA from precursors, purity and particle size of the obtained HA powders were evaluated. HA derived from the precursor with CA showed a different transformation process from that without CA. It was observed that the content of CaO as an unavoidable major impurity was reduced due to the addition of CA. In the calcined powders from the CA-free precursor, X-ray diffraction (XRD) patterns revealed an intense CaO peak. For the calcined powders from the CA-addition precursor, XRD analysis showed a very weak CaO peak. It was also found that the synthesized HA powders from precursor with CA were finer than those without CA. The mechanism of the influence of CA on the formation, purity and particle size distribution of HA powders was discussed.