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The structural phases observed in LiKSO4 crystals due to thermotropic transitions have been studied for more than a century. Nowadays many different phases are referenced, but some of the results are still controversial. Structural studies by single-crystal X-ray diffraction from room temperature to 803 K are presented here. Phase II (708 < T < 943 K) is extensively discussed on the basis of ordered and disordered models, using harmonic and anharmonic atomic displacements, and considering a twinned crystal composed of three orthorhombic domains. Analyses of the same phase at different temperatures determine the best structure model. [References: 36] 36