Mn-ion doped calcium phosphates namely Ca 5(PO 4) 3(OH) hydroxyapatite (HAP), β-Ca 3(PO 4) 2 (β-TCP) as well as Ca 9.5Mn(PO 4) 7 whitlockite were synthesized and the optical properties of the Mn 2+ cations were investigated. Annealing under reducing atmosphere enhances the emission of the divalent manganese species. Electron paramagnetic resonance (EPR) and optical spectroscopies confirm that Mn 2+ ions are the active species. Orange and red emissions occur respectively for the Mn:HAP and Mn:TCP. For this latter, long-lasting phosphorescence (LLP) coming from the Mn 2+ emission ( 4T 1 → 6A 1 transition) is observed at 640 nm but it appears that the traps depths are either two shallow or too deep to lead to an efficient long-lasting emission.