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Sodium-bismuth titanate Na0.5Bi4.5Ti4O15 (NBT) and barium bismuth titanate BaBi4Ti4O15 (BBT) and their solid solutions were prepared by solid state reaction of the constituent oxides. The room temperature structural characteristics were determined by X-ray diffraction and the dielectric properties investigated in a wide range of temperatures (20–750°C) and frequencies (1 kHz–1 MHz). As the barium content increases, the unit cell change from orthorhombic to pseudo-tetragonal, the paraelectric to ferroelectric phase transition decreases from 655°C to 400–420°C and a relaxor-like behaviour is observed for high barium contents. Depending on the composition, dielectric data were fitted using both classical (low Ba) and modified Curie-Weiss law for relaxors (high Ba).