Phase transformation of calcium phosphates from amorphous to crystalline phases around neutral pH proceeds via direct structure conversion using non-ionic elementary units. This transformation inevitably forms metastable intermediate-structured phase(s) between the two end phases. In addition to conventional calcium phosphate phases appearing in the transformation, new unknown phases were observed. They did not correspond to simply poor crystalline materials of conventional phases and instead had particular structures. One was pseudo-OCP, which lacked the HPO 4 -OH layers in the conventional OCP structure.Keywords: Phase transformation; Amorphous phase; Intermediate phase; OCP; HAP Calcium phosphates have been energetically investigated for more than half a century because of their important role not only in forming hard tissues such as bone and teeth but also being a frequent cause of calculus and arteriosclerosis [1,2]. One factor hindering a sound understanding of their formation mechanism is that they appear in several forms at room to body temperatures [3,4]. For example, amorphous calcium phosphate (ACP), dicalcium phosphate dihydrate (DCPD), β-tricalcium phosphate (β-TCP), octacalcium phosphate (OCP), and hydroxyapatite (HAP) form in weak acidic to weak basic calcium phosphate solutions. They precipitate and stably exist or transform into other more stable phases depending on the solution conditions. Transformation between each calcium phosphate [5][6][7] is of particular interest because the control of this process results in obtaining a desirable phase that can contribute to the design of calciumphosphate-based biomaterials with novel functions.Two phase-transformation mechanisms have been proposed. One is solvent-mediated transformation, which is the simple dissolution and growth of materials depending on the difference in solubility. A representative example for calcium phosphate is the hydrolysis of DCPD and subsequent growth of OCP [8]. The other is structural conversion from metastable to stable phases as was revealed in situ using a light scattering technique [9,10]. If the concentrations of calcium and phosphate ions in the solution are sufficiently high, ACP first forms in the solution and transforms into other phases such as OCP and HAP. The transformation proceeds via direct conversion of an amorphous structure into crystalline ones. This kinetics is attributed to a common cluster unit present in both the amorphous and crystalline phases [11][12][13][14][15]. Posner's cluster [11] and its symmetric isomers [16] were proposed for this common cluster, and then more complex structures of clusters were found through experimental and computational investigations [17,18]. That the clusters can be decomposed into smaller ion pairs as the minimum unit was also proposed [19], indicating the need for more careful investigation of the elemental unit in the phase transformation of calcium phosphates.Leaving aside the question about the structure of the minimum unit, we note that it is well accepte...