The influence of synthesis conditions on the development, thermal behavior, and sintering characteristics was investigated for nano- and macro-crystalline Bi5FeTi3O15-based ceramic materials with a perovskite-like four-layered Aurivillius phase structure. It was shown that the start of grains sintering corresponds with the start of surface phase melting, given that the surface phase composition can be controlled by changing the chemical composition of the initial mixture. The temperatures of crystallization, phase transition, decomposition, sintering activation of the produced materials were determined along with the thermal coefficient of their linear expansion.