Beta‐tricalcium phosphate (β‐TCP) powder doped with metal (Na+ or Mg2+) ions was prepared using a novel polymerized complex method that involves a reaction between metal ions and an organophosphorus chelating agent [(2‐phosphonobutane‐1.2.4‐tricarboxylic acid (PBTA)]. The precursors were uniformly gelled by the chelation and dehydration condensation of the carboxyl groups and phosphonic acid groups in PBTA, and metal (Ca2+, Na+, and Mg2+) ions. When precursors with/without Na+ ions were used, the β‐TCP phase crystallized through the α‐TCP phase, whereas when precursors containing Mg2+ ions were used, it crystallized directly. The crystallization temperature of the β‐TCP phase from the precursors decreased with the addition of Na+ and Mg2+ ions. The lattice constants of each sample after heating the precursors at 1000°C were almost the same as those of β‐TCP powder doped with metal ions via a solid‐state reaction. The synthesized samples also had a stoichiometric composition. Heating the precursors above 550°C resulted in a unique chain structure, which remained unchanged even after the addition of Na+ and Mg2+ ions. However, at the same heating temperature, the particle size of the samples increased with the addition of Na+ ions, but decreased with the addition of Mg2+ ions.