The red long-lasting phosphorescent (LLP) ofβ-Zn3(PO4)2:Mn2+,Pr3+ material was prepared through combustion and con-ventional solid-state sintering methods. The influence of Pr3+ ions on luminescence and LLP of Mn2+ inβ-Zn3(PO4)2:Mn2+,Pr3+ phos-phor was systematically investigated. The phosphor presented a strong photoluminescence peak at 620 nm attributed to the4T1g→6A1g transition of Mn2+ ions in octahedral coordination. Red LLP was observed inβ-Zn3(PO4)2:Mn2+,Pr3+ phosphors with persistence time for more than 2 h. It was found that the long persistent phosphorescent performance of Mn2+ such as brightness and duration was improved by the energy transfer from Pr3+ to Mn2+ when Pr3+ ions as sensitizers were doped into matrix. The fact that the TL peak at low temperature was largely enhanced in Mn2+, Pr3+ codopedβ-Zn3(PO4)2 phosphor showed the significant increase of defect concen-tration with suitable depth. There existed two factors working together to be responsible for the enhancement of LLP performance inβ-Zn3(PO4)2:Mn2+,Pr3+.