One of the appealing areas for fundamental research from the perspective of materials science is the influence of dynamic shock waves on crystals and the study of their structural responses. In the current work, we have reported the impact of shock waves on technologically important lithium sulphate monohydrate (LSM) single crystal with (101) orientation and powder X-ray diffraction (PXRD), optical and Raman spectroscopy, scanning electron microscope (SEM) techniques have been utilized to examine the structure–property relationship of the title crystal at shocked conditions. Interestingly, we have found that the crystalline perfection of the crystal has greatly improved at shocked conditions. The optical transmittance is also found to be massively increased at shocked conditions and found the values to be 40 and 60% at 500 nm for control and shocked crystal, respectively. The structure–property relationship of the enhancement of the degree of crystalline nature and optical properties is discussed. It is to be noted that, the enhancement of 20% in optical transmittance at 1 shocked condition is never been reported for any crystal so far. Raman spectral analysis and SEM results are also provided the supporting shreds of evidence for the enhancement of the crystalline perfection at shocked conditions. Due to the high degree of crystalline perfection and high optical transmittance, the shocked crystal is highly favourable for photonic applications.