AbstractDicalcium silicate, which is found in steelmaking slag for dephosphorization, exists as the hexagonal α phase at high temperatures. The α‐dicalcium silicate forms a solid solution with tricalcium phosphate in the entire composition range, although the reason for high solubility of phosphorus remains unclear in view of the crystal structure. It has previously been reported that the crystal structure of α‐dicalcium silicate consists of a symmetric arrangement of Ca2+ ions and SiO44− tetrahedra, although other polymorphs exhibit asymmetric arrangements. However, because the occupation probability of each atomic site in the α polymorph is not limited to unity, it has not been qualified how these ions are exactly arranged. In this study, the ionic distribution in the α polymorph of dicalcium silicate was evaluated by first‐principles calculation based on density functional theory (DFT), as well as by molecular dynamics (MD) simulation with a polarizable ion model optimized by DFT calculation. The results indicated that the completely symmetric ionic arrangement, as reported for the α phase, is the most unstable. Electronic‐state calculation and MD simulation indicated that a highly disordered ionic arrangement spontaneously forms in the α‐phase crystal for structure relaxation when held at high temperatures, or when phosphorus is incorporated.