Benzodithiophene (BDT) was symmetrically bisubstituted in the terminal positions with five different alkynes C≡C-(C(n)H(2n+1)) with n = 4, 6, 8, 10, 12. The materials were characterized as potential materials for field-effect transistor applications. Electrochemical measurements in solution and photophysical measurements in solution and in the solid state, together with UV photoelectron spectroscopy in air and quantum-chemical calculations, elucidate the nature of the frontier orbitals and of the excited states as well as their deactivation pathways. Structural information on the molecular assembly in the solid state, both at room temperature and at elevated temperatures, is obtained by a combination of DSC, polarized optical microscopy, and 2D-WAXS, which point to the crystallinity of the compounds in all phases and reveal π-stacking arrangements independently of the length of the alkyl side chains.