Rietveld analysis on X-ray powder diffraction patterns recorded from Zn-doped, Zn/Sr, and Zn/Mg codoped biphasic calcium phosphate (BCP) samples has been used to locate Zn2+ cations in both hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) phases heat-treated at 1100 °C. Zn atoms occupy interstitial sites in HAp (Wyckoff site 2b), leading to an insertion solid solution of general composition Ca10Znx(PO4)6O2x(OH)2–2x. Replacement of hydroxyl by O2– anions with formation of linear O–Zn–O entities should be considered to preserve the electroneutrality of the material. Contrary to HAp case, Zn atoms substitute calcium atoms in β-TCP leading to a substitution solid solution of general composition Ca3–xZnx(PO4)2. Micro-Raman spectroscopy and neutron diffraction have confirmed these insertion/substitution mechanisms. The different mechanisms of zinc incorporation should be considered to stabilize the desired calcium phosphate phase which are managed by the Ca/P and (Ca+Zn)/P ratios. Furthermore, discussion of biological properties of Zn-doped calcium phosphate ceramics should take into account the true insertion mechanism as critically discussed here.Keywords: biomaterials; zinc doping; calcium phosphates; Rietveld refinement; Raman