For thermoelectric materials, the figure of merit depends on the nanostructure, morphology, element doping, and the structure of the interface with other materials. Control of this interface is important in relation to a wide range of thermoelectric material designs such as in organic–inorganic hybrid compounds. Therefore, we evaluated the ease of forming various Bi2Te3 (0 0 1) termination surfaces using formation energy and calculation of phonon dispersion after structure optimization; TeI-1 and TeII terminations exhibited static and dynamic stabilities within various termination structures. In density-of-state and charge-distribution calculations, the TeII termination form exhibited distinctive electronic states around the Fermi energy that originated from the exposed Te atoms; therefore, it is suggested that efficient carrier transfer shall occur at the interface between a TeII surface and another material.