Abstract The thermal properties of compounds of the general formula Bi m 1 Fe m − 3 Ti3O3m 3, which are layered perovskite-like phases of the Aurivillius type, are investigated as a function of their composition. It is demonstrated that the temperature of decomposition of the Bi m 1 Fe m − 3 Ti3O3m 3 compounds decreases with an increase in the thickness of perovskite-like layers alternating in the structure and that the composition dependence of the temperature of the structural transition observed in these compounds exhibits a more complex behavior. The linear thermal expansion coefficients of all the compounds under investigation are found to be virtually independent of the composition.