Tb 3+ /Sm 3+ single as well as co-doped LaMgAl11O19 (LMA) phosphors have been synthesized by a low-temperature solution combustion method. The X-ray diffraction pattern, photoluminescence properties and energy transfer (ET) processes between rare earth (RE) ions, were investigated in detail. The mechanism of energy transfer (ET) from Tb 3+ to Sm 3+ was seen as the dipole–dipole interaction. Efficient ET from Tb 3+ to Sm 3+ ions was observed, leading to color-tunable emissions of LMA:0.02Tb 3+ , x Sm 3+ (x = 0.005 to 0.02 mol) phosphors. The efficiency of the ET gradually increased with increase in the Sm 3+ ion concentration, reaching a maximum of 78.28% at Tb 3+ ion concentration 0.02mol. The critical distance (Rc) among sensitizer and activator by the concentration quenching method was estimated to be 27.96 Å. The LMA: Tb 3+ , Sm 3+ phosphors exhibited the emission peaks in the blue ( 5 D3→ 7 FJ = 5, 4, 3, and 2), green ( 5 D4→ 7 FJ = 6, 5, and 4), and orange-red ( 4 G5/2→ 6 HJ = 5/2, 7/2, and 9/2) regions under the excitation wavelength of 375 nm. As a consequence of fine-tuning of the emission composition of the Tb 3+ and Sm 3+ ions, multicolor emitting luminescence properties can be achieved in a single host lattice LMA.