The Aurivillius phases (APs) [Bi2O2]2+[Am−1BmO3m+1]2− are well-known ferroelectrics with high Curie temperatures. High-temperature piezoceramics Bi3−xGdxTiNbO9(BiGdTiNb, x=0, 0.1, 0.2, 0.3) were prepared by a solid-state reaction method. The structural and electrophysical characteristics of BiGdTiNb ceramics have been studied. According to the data of powder X-ray diffraction, all the compounds are single-phase with the structures of two-layer APs (m=2) with the orthorhombic crystal lattice (space group A21am). The temperature dependence of the relative permittivity ε∕ε0 (T) of the compounds was measured and showed that the Curie temperature of perovskite-like oxides Bi3−xGdxTiNbO9 increases linearly with an increase in the substitution parameter x to TC=950∘C. The activation energies of charge carriers have been found in different temperature ranges.