A new class of oligothiophene–anthracene co-oligomers, 9,10-bis(2-dodecyloligothienylvinyl)anthracene T_nA (n = 1, 2 and 3), were synthesized and characterized. The photophysical and electrochemical properties of these oligomers demonstrated an increased conjugation length with increasing number of thiophene units. These oligomers also exhibited relatively larger ionization potential values compared with pentacene and sexithiophene and thus are expected to show improved stability. The strong aggregation tendency and excimer formation for T₁A and obvious aggregation effect for T₂A in solution were observed from the concentration and temperature-dependent fluorescence spectra. In contrast, no obvious aggregation behavior could be observed for T₃A in solution. Thermal behavior and self-assembly of these co-oligomers in solid state were studied by a combination of TGA, DSC, powder X-ray diffraction and polarizing optical microscope. Liquid crystalline phases were observed in T₂A and T₃A at elevated temperature while only a crystalline phase was found for T₁A. Single-crystal structures of T₁A and T₂A revealed a lamellar packing mode with ordered intermolecular anthracene-to-anthracene and oligothiophene-to-oligothiophene π–π stacking and these qualify them as potential semiconductors in electronic devices.