Structure, photoluminescence, colorimetric, and thermoluminescence analysis of Ca1-x-yTb2x/3Sm2y/3WO4; x = 0.01; y = 0.01-0.05 ceramics are reported in this manuscript. The materials are made by the use of the solid-state method. Reitveld refinements of the obtained X-ray diffraction patterns are done by using the Fullprof Suite software. The obtained results denoted that the synthesized materials have a tetragonal structure and I41/a space group. Energy bandgaps are found in the UV-visible absorbance spectra. Photoluminescence investigations of the phosphors are done. The critical quenching concentrations of the phosphor are found to be x=0.01; and y=0.04. Moreover, the critical distance of energy shift with the adjacently presented ions is computed. Dexter’s theory is employed to elucidate that the dipole-dipole electronic interactions are the imperative reasons for the transfer of energy in the phosphor. The white color of emission is achieved for x=0.01, y=0.04 Tb, and Sm doped CaWO4 material. Moreover, great values in color purity, correlated color temperature, color rendering index as well as luminous efficiency of radiation are obtained from the CIE Chromaticity coordinates. Quantum yield efficiency of x=0.01, y=0.04 Tb & Sm codoped CaWO4 is measured. Photoluminescence decay analysis of all the samples is done to study the long-after glow properties and also the average lifetime values are evaluated. This is an indication of the suitable usage of the prepared materials in the white light-emitting diodes. Concentration as well as dose-dependent Thermoluminescence spectroscopy is investigated thoroughly. Kinetic parameters are calculated by deconvoluting the spectra of x=0.01; y=0.01 Tb & Sm codoped CaWO4 irradiated with 15min of UV excitation dose. These results are denoted by high trap depth, second-order kinetics, and low UV dosimetry of the phosphor.