pi-Extended thieno[3,2-b] thiophene-containing aromatic compounds were developed as stable, high-performance organic semiconductors for organic thin-film transistor (OTFT) applications. Of them, dinaphtho[2,3-b:2 ',3 '-f] thieno[3,2-b] thiophene consisting of six aromatic rings gave high quality thin films by vapor deposition, which acted as a superior filed-effect transistor channel showing mobility as high as 3.0 cm(2) V-1 s(-1). On the other hand, highly soluble 2,7-dialkyl[1] benzothieno[3,2-b][1] benzothiophenes gave solution-processable OTFTs with mobility higher than 1.0 cm(2) V-1 s(-1). (C) 2013 Elsevier B.V. All rights reserved.