Ce3+ ion doped olgite mineral samples, Na(Sr, Ba)PO4, were prepared by a high temperature solid-state reaction. The sample was investigated through x-ray powder diffraction, FT-IR and FT-Raman spectra measurements. The optical properties under vacuum ultraviolet (VUV) synchrotron radiation and ultraviolet (UV) irradiation are reported for the first time. The investigated samples show a strong absorption in the VUV and UV ranges. The bands corresponding to the 4f1 → 4f05d1 transitions of Ce3+ ions in the host lattices are identified. The barycentre of Ce3+ ions in the host lattices, the host absorption, the crystal field splitting, the emission and the Stokes shifts are presented and discussed. This Ce3+ ion doped material is a potential candidate for plasma display panel (PDP) application.