Abstract α-tricalcium phosphate (α-TCP), biphasic α/β-tricalcium phosphate (α/β-TCP) with different two phase ratio and β-tricalcium phosphate (β-TCP) powders were prepared by calcining an amorphous calcium phosphate (ACP) precursor at a temperature ranging from 800 to 900 °C. The microstructural characterization revealed that the particles in the monophasic and the biphasic TCP powders had about 1 μm in size, and agglomerated by 500 nm ones. In comparison with monophasic TCP powders, the dissolution–reprecipitation behaviors of the biphasic TCP powders in an acetate buffer solution with pH 5 were studied. The biphasic TCPs demonstrated a different behavior from the monophasic TCPs, including changes in morphology and crystalline phase. The unique behavior can be tailored by controlling the α-TCP content in the biphasic TCP powders.