We investigate the photoluminescence (PL) and photoluminescence excitation (PLE) spectra of 20Al(PO3)3-80LiF+Pr glass (APLF+Pr) and Pr3+-doped LiCaAlF6 crystal (Pr:LiCAF) in order to determine the electronic states of Pr3+ in APLF glass host and to improve APLF+Pr scintillation properties. Ultraviolet (UV) emission bands at around 250 and 340 nm were observed from both materials and these can be ascribed to 4f5d → 4f2 transitions in Pr3+. Emission at around 400 nm was also obtained and is principally attributed to 1S0 → 4f2 transition. Difference in the emission profiles of these two materials was found to be due to the extent of the 5d band and its position relative to the 1S0 state. Increasing the concentration of Pr3+ up to 2 mol% was found to improve UV emission ratio due to the faster cross-relaxation of 4f states. This could improve the quantum efficiency of APLF+Pr as a neutron scintillator for scattered-neutron diagnostics in laser fusion research.