A slow evaporation solution growth technique is used to grow rare earth (Eu3+ and Tb3+) doped lithium sulfate monohydrate (LSMH) single crystals. X‐ray diffraction analysis of these crystals confirms the monoclinic crystal structure with P21 space group. Energy dispersive X‐ray spectroscopy is used to check the incorporation of dopants into the crystal lattice of these LSMH crystals. Dielectric, UV–vis photoluminescence spectroscopy studies are carried out to study the electrical and optical behavior of these crystals. The optical bandgap decreases by doping and the current material follows the direct allowed transition. The dielectric constant and ac conductivity slightly increase with the incorporation of Eu3+ and Tb3+ ions in the crystal matrix. The effect of doping on the functional groups of LSMH crystals is confirmed by Fourier transform infrared spectroscopy. The micro‐Raman spectroscopic technique is carried out on these samples, confirming the stress experienced by the crystal with dopants, and further leading to the degradation of the crystal structure. The photoluminescence emission with a large decay time of the as‐grown crystals is dominated by the 5D0 → 7Fj transitions of Eu3+ and 5D4 → 7Fj transitions of Tb3+ ions, and further provides a possibility of using them as potential optical materials.
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