Nano-sized zinc-substituted hydroxyapatite (nano-ZnHA) has stimulatory effect on bone formation and inhibitory effect on osteoclastic bone resorption in vivo. Nano-ZnHA with serial zinc fractions (0, 2, 5, 10 mol%) were synthesized by an improved precipitation method based on dialysis process. Transmission electron microscopy observation indicated that the increase of Zn fraction led to smaller crystallite. X-ray diffraction of the products revealed that some typical characteristic peaks of HA displayed when the Zn fraction was below 10%. Fourier transform infrared spectroscopy showed that the bending peaks of the group-OH in HA became wider with the increase of Zn fraction and it disappeared at 10 mol%. The current work demonstrated that zinc could substitute for calcium into hydroxyapatite in the limited range of composition by using dialysis process.