A novel synthesis of nano-fluoride-substituted hydroxyapatite (nano-F-HAP) was successfully realized through dialysis process within 4 h, which required much shorter time than the methods reported so far. In new preparation, a dialysis was employed to purify unwanted ions. The removal efficiency of impurity ions in dialysis was evaluated by calculating the concentration of the representative irons NH4 + between the inner slurry and outer distilled water. Results showed that total dialysis efficiency came to 94.5%. The final products were characterized by XRD, HR-TEM, and FT-IR. The XRD and FT-IR results strongly supported substitution of F- for OH-, and the TEM pictures further indicated that the final crystals are about 100nm in length and about 20 nm in diameter without obvious aggregation. Therefore, comparing with traditional purifying processing, such a new synthesis provides a promising application for scale preparation of fine nano-F-HAP crystals.