Rare earth doped compositions Na3-3xLnxFe2(PO4)3 (x = 0, 0.025, 0.05, 0.075 and 0.1) were prepared by ion-exchange method using Na3Fe2(PO4)3 and LnCl3 (Ln = Eu and Tb). Pristine Na3Fe2(PO4)3 was obtained by ethylene glycol assisted gel burning procedure. The phase characterization was performed by powder X-ray diffraction (XRD). All the compositions were well crystalized in monoclinic lattice. The FE-SEM images and elemental mapping were obtained. The infrared and Raman profiles of all-compounds were dominated by the bands owing to the (PO4) units. Investigation on photoluminescence emission and excitation spectra of Ln3+ (Ln = Eu, Tb) were carried out. The excitation spectra of Na3-3xLnxFe2(PO4)3 (Ln = Eu and Tb) gave intensive band at 256 (370) nm for Eu (Tb) doped phosphors. The photoluminescence emission spectra of Ln3+ (Ln = Eu, Tb) were carried out. The emission spectra of these composition were characterized by f -f transitions corresponding to 613 (5D0→7F2) for Eu and 543 (5D4→7F5) for Tb doped compositions. The maximum emission intensity for Eu (Tb) doped phosphors was found at x = 0.075 (0.05). The analysis of CIE and CCT values of all prepared phosphors were also carried out. Decay curves were analyzed in detail. The visible-light photo-catalytic activity of parent Na3Fe2(PO4)3 was examined against decomposition of methylene blue and methyl orange dyes. Parent Na3Fe2(PO4)3 exhibits good efficiency against MB (≈94.5 %) and moderate efficiency against MO (≈64 %) in 180 min of visible light irradiation. Scavengers’ experiments were carried to identify the active species during photodegradation.