In present work, KNa(SO4 ) phosphors doped with different concentrations of rare earth Eu3+ , Sm3+ and Dy3+ ions (0.05, 0.1, 0.3, 0.5, 0.7, 1 mol%) were synthesized using a solid-state diffusion technique. Photoluminescence (PL) investigations were carried out for the whole range of Eu3+ , Sm3+ and Dy3+ -doped phosphors; rare earth ions that retained maximum PL intensity were selected for advanced anionic exchange. In the present investigation, phosphors KNa(SO4 ):Eu3+ (1 mol%), KNa(SO4 ):Dy3+ (0.5 mol%) and KNa(SO4 ):Sm3+ (0.3 mol%) had the highest PL intensity, and were therefore selected for further anionic substitution of sulphate anions with different concentrations of vanadate, phosphate, and tungstate anions, such as KNa(SO4 )1-x (MO4 )x : W (where W = Eu3+ 1 mol%, Dy3+ 0.5 mol% and Sm3+ 0.3 mol%; MO4 = PO4 , VO4 , WO4 ; and x = 0.1, 0.3, 0.5, 0.7, 1). Structural and molecular environments of the substituted phosphors were characterized individually using X-ray diffraction and Fourier transform infrared spectroscopy. In-depth morphological investigations of the prepared phosphors were undertaken using scanning electron microscopy. For the principal investigation on enhancement of white light-emitting diode (w-LED) performance, the PL properties of all the synthesized phosphors were studied analytically. Emission intensity ratios for KNa(SO4 ):Eu3+ 1 mol%, KNa(SO4 )0 (PO4 )1 :Eu 1 mol%, KNa(SO4 )0.9 (VO4 )1 :Eu 1 mol%, and KNa(SO4 )0.9 (WO4 )0.1 :Eu 1 mol% were 1:1.15:1.23:0.08. PL intensity ratios for the phosphors KNaSO4 :Dy 0.5 mol% and KNa(SO4 )0.9 (PO4 )0.1:Dy 0.5 mol% was 1:2. The ratio of PL intensity was 1:3.2:0.8 for KNa(SO4 ):Sm 1 mol%, KNa(SO4 )0.5 (PO4)0.5 :Sm 0.3 mol%, and KNa(SO4 )0.7 (VO4 )0.3 :Sm 0.3 mol% phosphors, respectively. Chromaticity investigations were carried out using Commission Internationale de l'Éclairage colour co-ordinate diagrams, which suggested that the prepared Eu3+ -doped and Sm3+ -doped phosphors would be prospective candidates for red and green LEDs, respectively, whereas Dy3+ -doped phosphors showed emission in the blue and yellow regions. The entire study indicated that amalgamation of anionic exchange at a KNaSO4 phosphor activated with Eu3+ , Dy3+ and Sm3+ rare earth ions could generate and enhance white light emission.