The semi‐empirical tight‐binding (TB) method within the sp3s* basis has been used to investigate the electronic structure and optical properties of silicon carbide (SiC) polytypes. A TB model for the electronic structure calculations of the (4H, 6H and 8H) SiC polytypes is presented. The procedure involves the construction of the TB Hamiltonian of the (4H, 6H and 8H) SiC polytypes from the wurtzite one. The set of TB parameters is transferable to all hexagonal structures, which overcomes the need for extensive experimental data. The band structures for different SiC polytypes are used to determine the electron effective masses. The results are shown to be consistent with available experimental data and other theoretical calculations. Furthermore, the joint densities of states are calculated. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)