High performance piezoelectric ceramics with high Curie temperatures ( T C) are the bottle necks of relevant high temperature devices. In this study, the electrical performance and microstructure of Li and Mn codoped Aurivillius-type composite ceramics with a composition Ca0.99 - x Bi6.99+ x (LiMn)0.01NbTi5O24 ( x = 0–0.8) were systematically investigated. The results indicated that uniform intergrowth structure with a lattice similar to that of the end member CBT could be formed at a low x value ( x d 33 values about 2 to 3 times of that of the constituent phase CaBi4Ti4O15 and Bi3TiNbO9 with still a high depolarization temperature. The performance of the samples was found to be related to the density and larger lattice distortion along the polarization a axis. The results also demonstrated that formation of the compound system was an effective way in improving the performance of Aurivillius-type high T C piezoelectric ceramics.