A condensed benzothiophene peripherally carrying rich sulfur atoms favoring pi-pi stacking is developed through facile approaches. The H-1 NMR and the absorption spectra strongly indicate that this molecule easily forms the self-assembled structures in solutions. Microwires directly precipitate from solution, and such 11) self-assembled nano-and microstructures can be controlled and tuned by changing solvents and casting on various substrates. Single microwire transistor based on such condensed benzothiophene is easily fabricated through solution process with carrier mobility as high as 0.01 cm(2) V-1 S-1.