Several bismuth layer-structured compounds An−3Bi4TinO3n+3 (A = Ba, Sr, Ca) with n > 4 were synthesized and investigated. The average radius of A-site cations was found to be closely related to the lattice parameters in the a–b plane and, therefore, closely related to the stability of the layer structure. For Ba2Bi4Ti5O18 ceramics, there was a diffused phase transition centered at approximately 330 °C, which should be due to the cation redistribution of A-site Ba2+ and Bi3+ in the (Bi2O2)2+ layer. For Sr2Bi4Ti5O18 ceramics, a sharp dielectric constant peak was found at 325 °C. Ceramics of five-layered Ca2Bi4Ti5O18 and six-layered Ca3Bi4Ti6O21 showed temperature-stable dielectric constants up to 800 °C, and ferroelectricity was observed. In addition, as ferroelectrics, these Ca-containing bismuth layer-structured compounds showed frequency-independent dielectric constants >150 and small tan δ on the order of 10−3–10−4 in the frequency range of 1 kHz to 1 MHz.