β-Ca3(PO4)2-type phosphors Ca9−xMnxEu(PO4)7 have been synthesized by high-temperature solid-phase reactions. The crystal structure of Ca8MnEu(PO4)7 was characterized by synchrotron X-ray diffraction. The phase transitions, magnetic and photoluminescence (PL) properties were studied. The abnormal reduction Eu3+ → Eu2+ in air was observed in Ca9−xMnxEu(PO4)7 according to PL spectra study and confirmed by X-ray photoelectron spectroscopy (XPS). Eu3+ shows partial reduction and coexistence of Eu2+/3+ states. It reflects in combination of a broad band from the Eu2+ 4f65d1 → 4f7 transition and a series of sharp lines attributed to 5D0 → 7FJ transitions of Eu3+. Eu2+/Eu3+ ions are redistributed among two crystal sites, M1 and M3, while Mn2+ fully occupies octahedral site M5 in Ca8MnEu(PO4)7. The main emission band was attributed to the 5D0 → 7F2 electric dipole transition of Eu3+ at 395 nm excitation. The abnormal quenching of Eu3+ emission was observed in Ca9−xMnxEu(PO4)7 phosphors with doping of the host by Mn2+ ions. The phenomena of abnormal reduction and quenching were discussed in detail.