The luminescence centers in antimony doped fluorapatite phosphors were characterized by optical emission spectroscopy, IR and FTIR absorption, and Raman scattering. The luminescence centers in commercial phosphors consist of covalently bound Sb-O pairs (N center). The vibrational spectrum of analogous Bi-O pairs was studied for the first time in FAP. New methods of preparation yielded material with a record high level of Sb-O doping. There is a second well established (HE) center which consists of Sb on Ca2 sites and Na at nearby Ca1 or Ca2 sites. The properties of the N and HE centers differ greatly and are described in detail. We showed for the first time that HE centers like N centers can efficiently sensitize the fluorescence of manganese in FAP.