Phosphate glasses in the compositions of 70P 2 O 5 –15Al 2 O 3 –14Na 2 O–1RE 3+ (RE=Sm, Dy, and Tm) (mol%) were prepared by melt-quenching technique and characterized optically. The differential thermal analysis (DTA) profile of the host glass was carried out to confirm its thermal stability. For all the glasses absorption, photoluminescence and decay measurements have also been carried out. These glasses have shown strong emission and absorption bands in visible and near-infrared (NIR) region. From the measured absorption spectra, Judd–Ofelt (J–O) intensity parameters (Ω 2 , Ω 4 and Ω 6 ) have been calculated for all the studied ions. For Sm 3+ doped glass, four emission bands centered at 562nm ( 4 G 5/2 → 6 H 5/2 ), 598nm ( 4 G 5/2 → 6 H 7/2 ), 644nm ( 4 G 5/2 → 6 H 9/2 ), and 704nm ( 4 G 5/2 → 6 H 11/2 ) have been observed with 402nm ( 6 H 5/2 → 4 F 7/2 ) excitation wavelength. Of them, 598nm ( 4 G 5/2 → 6 H 7/2 ) has shown a bright orange emission. With regard to Dy 3+ doped glass, a blue emission band centered at 486nm ( 4 F 9/2 → 6 H 15/2 ) and a bright yellow emission at 575nm ( 4 F 9/2 → 6 H 13/2 ) have been observed, apart from 662nm ( 4 F 9/2 → 6 H 11/2 ) emission transition with an excitation at 388nm ( 6 H 15/2 → 4 I 13/2 , 4 F 7/2 ) wavelength. Emission bands of 650nm ( 1 G 4 → 3 F 4 ) and 785nm ( 1 G 4 → 3 H 5 ) transitions for the Tm 3+ doped glass, with an excitation wavelength at 466nm ( 3 H 6 → 1 G 4 ), have also been observed. The stimulated emission cross-sections of all the emission bands of RE 3+ glasses (RE=Sm, Dy, and Tm) have been computed based on their measured full-width at half maximum (FWHM, Δλ) and measured lifetimes (τ m ).