A novel semiconductor with naphtho[2,3-b]thiophene rings was synthesized and characterized by using single crystal X-ray structure analysis, absorption and emission spectra, electrochemical measurements, quantum chemical calculations, thin-film X-ray diffraction and AFM studies. FET devices using the molecule as the active layer showed high mobilities and high air stability. The hole mobility was enhanced to 0.67 cm2V−1 s−1 in air.