Materials with a layered perovskite-like structure of the Aurivillius phase type are important for technology fields such as magnetoelectronics and photocatalysis. Features of phase formation during the synthesis of nano- and macrocrystalline materials based on Bi6Fe2Ti3O18 with the five-layer Aurivillius phase structure are described. Samples were characterized by powder XRD, DSC/TG, dilatometry, and SEM/EDX. The temperatures of the beginning of formation, the Curie point, the beginning of decomposition and activation of sintering of the obtained materials, and the value of the coefficient of linear thermal expansion were determined. The technological possibility of controlling the dispersion of the obtained materials by changing the synthesis conditions is shown.