This study reports a novel method for the preparation of several biologically important calcium phosphate (Ca-P) phases such as hydroxyapatite (HA), dicalcium phosphate dihydrate (DCPD) and dicalcium phosphate anhydrous (DCPA). X-ray diffraction (XRD) results showed that phase pure DCPD, DCPA and HA nano-crystals could be produced in the Ca2+/PO4 3- solutions with the presence of EDTA at 120 oC, 180 oC and 210 oC, respectively. Transmission electron microscope (TEM) micrographs revealed that all the Ca-P precipitates were needle-like or rod-like. Most of the precipitates ranged from 100 ~ 200 nm in length. Selected area electron diffraction confirmed that the longitude direction of the rod-like HA precipitates were along c-axis and the flat surface was (110). Thermal gravimetric analysis of the DCPD precipitates revealed that phase transformations of DCPD to DCPA and DCPA to HA occurred at 139 oC and 195 oC, respectively, which resulted in the different Ca-P phases during hydrothermal synthesis at different temperature ranges.