Here we discuss requirements for high performance and solution processable organic semiconductors, by presenting a systematic investigation of 7-alkyl-2-phenylbenzothieno[3,2-b]benzothiophenes (Ph-BTBT-C
’s). We found that the solubility and thermal properties of Ph-BTBT-C
’s depend systematically on the substituted alkyl-chain length n. The observed features are well understood in terms of the change of molecular packing motif with n: The compounds with n ≤ 4 do not form independent alkyl chain layers, whereas those with n ≥ 5 form isolated alkyl chain layers. The latter compounds afford a series of isomorphous bilayer-type crystal structures that form two-dimensional carrier transport layers within the crystals. We also show that the Ph-BTBT-C10 afford high performance single-crystalline field-effect transistors the mobility of which reaches as high as 15.9 cm2/Vs. These results demonstrate a crucial role of the substituted alkyl chain length for obtaining high performance organic semiconductors and field-effect transistors.