A benchmark of TD-DFT, wave function-based and semiempiric methods was performed for the geometries and excitation energies of diverse molecular organic semiconductors with varying polarity. Geometries were bench-marked by means of RMSD (root-mean-square deviation) values and MAE (maximum absolute error) values of geometric parameters specific for the electronic structure of the respective molecule. MS-CASPT2 calculations were used to benchmark excitation energies with respect to a confidence interval around the values obtained with CASPT2. The effect of spin-component scaling (SCS) on several wave function-based methods was thoroughly evaluated.