Stille coupling of 2-and 3-(tributylstannyl)thiophene derivatives with tetrabromobenzene followed by oxidative cyclization provides a simple, two-step synthetic route to two isomeric tetrathienoanthracene structures (13 and 14). The materials are characterized by a remarkable thermal stability, both in air (T dec ≈ 400 °C) and under nitrogen (sublimed with no decomposition at 450–500 °C). Optical studies of the parent and alkylated compounds showed sky-blue photoluminescence with quantum yields ranging between 0.17 and 0.40 and Stokes shifts of 0.03–0.16 eV. Both the optical properties and electrochemical behavior depend strongly on the position of the heteroatoms. Structural studies with X-ray crystallography (for 3D single crystals) and scanning tunneling microscopy (for 2D monolayers) indicate a high level of order, with similar intermolecular interactions for both isomers. The alkylated materials 13b and 14b have been used to fabricate thin-film transistors by both vacuum evaporation and solution processing. The preliminary studies show (unoptimized) hole mobilities of up to 7.4 × 10 -2 cm 2 V -1 s -1 and very high on/off ratios of up to 1 × 10 8 for vacuum-deposited films. The isomer 13, which showed higher thermodynamic stability of the radical cation and stronger intermolecular S · · · S contacts, also revealed better device performance.