Tetrathiafulvalene (TTF) was one of the most widely studied heterocyclic systems. However, TTF itself was easily oxidized, which induced the low stability and limited its potential applications. Here, a TTF derivative, 2,3,6,7-tetrakis(2-cyanoethylthio)tetrathiafulvalene (TCE-TTF), was synthesized. It was found that single crystalline micro- and nanowires of TCE-TTF were easily obtained by simple casting due to the enhanced π–π overlapping and S⋯S interaction. The thermal and vacuum stability analyses revealed TCE-TTF was much better than TTF. Single crystalline micro- and nanowires field-effect transistors were also fabricated by in situ dropping method. The typical mobility and on/off ratio were ∼0.02cm 2 /Vs and ∼10 3 , which predicted great potential applications of organic nanowires electronics.