Despite the progress, nanostructured calcium phosphates have the potential to improve the field of hard tissue engineering. Amorphous calcium phosphates with Ca/P molar ratio near 1.67 and 1.5 were synthesized by wet-chemical precipitation method and treated with ethanol. Upon thermal treatment, ACP clusters about 50 nm create a nanostructured HA or TCP. The highlights of this research: The precipitate treatment with ethanol provided a pure α-TCP that was found to be stable up to 1000 °C. HA is obtained from the ACP precursor synthesized using also ammonium dihydrogen phosphate.