The ability to control the molecular organization of electronically active liquid-crystalline polymer semiconductors on surfaces provides opportunities to develop easy-to-process yet highly ordered supramolecular systems and, in particular, to optimize their electrical and environmental reliability in applications in the field of large-area printed electronics and photovoltaics. Understanding the relationship between liquid-crystalline nanostructure and electrical stability on appropriate molecular surfaces is the key to enhancing the performance of organic field-effect transistors (OFETs) to a degree comparable to that of amorphous silicon (a-Si). Here, we report a novel donor-acceptor type liquid-crystalline semiconducting copolymer, poly(didodecylquaterthiophene-alt-didodecylbithiazole), which contains both electron-donating quaterthiophene and electron-accepting 5,5'-bithiazole units. This copolymer exhibits excellent electrical characteristics such as field-effect mobilities as high as 0.33 cm(2)/V.s and good bias-stress stability comparable to that of amorphous silicon (a-Si). Liquid-crystalline thin films with structural anisotropy form spontaneously through self-organization of individual polymer chains as a result of intermolecular interactions in the liquid-crystalline mesophase. These thin films adopt preferential well-ordered intermolecular pi-pi, stacking parallel to the substrate surface. This bottom-up assembly of the liquid-crystalline semiconducting copolymer enables facile fabrication of highly ordered channel layers with remarkable electrical stability.