The analysis of the solubility of MSO(4) in the high-temperature cubic modification of Li2SO4 reveals that divalent cations in the Li2SO4 structure can occupy either tetrahedral or octahedral positions. The former case is preferred for Be2+, and, to some extent, for Zn2+. For all the other divalent cations the octahedral positions are prefered in the formation of the alpha-Li2SO4-based solid solutions.