Herein, we report a case of A2MgWO6 (A = Ca, Sr, Ba) doped with 2%Dy3+, 2%Li+, in which the influences of the cation substitution are exhibited through the crystal structure, the charge transfer band (O2--W6+), the emission spectrum, the color of the luminescence, and the luminescent decay time. The substitution of Ca2+ and Sr2+ ions for larger ions (Ba2+) led to the crystal structure alteration from cubic to monoclinic and tetragonal, respectively. These structure changes also lowered the crystallography symmetry site of Dy3+, tuned the color of the emitted light from the whitish to yellowish region, and caused a blue shift of the CTB. Furthermore, a significant decline in the lifetime of the 4F9/2 → 6H13/2,15/2 transitions was noticed, from 748, 199, to 146 μs corresponding to Ba, Sr, Ca sample owing to the reduction in the local symmetry of Dy3+. Moreover, the thermal sensing properties of 2%Dy3+-doped samples were investigated based on the fluorescence intensity ratio technique in the range of 80-325 K. Under 266 nm excitation wavelength, the maximum relative sensitivity of the investigated samples was remarkably enhanced from 2.26%/K, 3.04%/K, to 4.38%/K corresponding to Ba, Ca, and Sr samples, respectively. In addition to providing a comprehensive understanding of the effects of compositional modifications on the optical properties, the results also present a viable pathway to manipulate the temperature sensing performance.