Slawsonite’s (SrAl2Si2O8) structure evolutions depending on temperature (27–1000 ℃) have been studied by in situ single-crystal X-ray diffraction. The SrO7 polyhedron expands regularly with the temperature increase. Silicon and aluminum cations are ordered in tetrahedral sites of the studied slawsonite; no significant changes in their distribution as temperature increases were observed. Slawsonite demonstrates a relatively high volume thermal expansion (αV = 23 × 10–6 °C–1) with high anisotropy, typical for framework feldspar-related minerals and synthetic compounds. It was found that, contrary to previously published data, the crystal structure of slawsonite is stable in the studied temperature range and no phase transitions occur up to 1000 °C. The role of Ca and Ba substitution for Sr and Al/Si ordering on polymorphism of natural MAl2Si2O8 (M = Ca, Sr, Ba) is herein discussed.