Several high Tc compounds containing Tl (thallium) were prepared starting from different initial compositions. Superconducting properties and the structure were determined for each sample. Electron diffraction and transmission electron microscopy showed the existence of polytypic high Tc compounds with the same a- and b-axes but different c-axis values. The c-axis appears to increase approximately in integral multiples of 0.15 nm with varying composition and is associated with the insertion of Cu–Ca or Cu–Tl layers in each unit cell. Several random stacking faults were also noted, which give rise to diffuse streaking in the electron diffraction pattern.