A new indolocabazole derivative possessing an extended aromatic core and solubilizing long aliphatic chains effectively self-assembles and crystallizes within the nanoscale channels to form single-crystal nanowires via a direct printing method from an ink solution. Single-crystal organic nanowire transistor arrays based on the π-extended indolocarbazole derivative exhibit an excellent hole mobility of 1.5 cm2 V-1 s-1 and outstanding environmental stability.