Mechanical compliance is a critical attribute for organic semiconductors in flexible, stretchable, mechanically robust, and biologically integrated electronics. This paper substantially develops the observation that a small change in the length of the alkyl side chain of regioregular poly(3-alkylthiophene)s has a dramatic effect on the interplay between their mechanical and charge-transport properties. Specifically, the thermal, mechanical, and charge-transport properties of poly(3-heptylthiophene) (P3HpT, n = 7), which we found to be an unusual example of a stretchable semiconducting thermoplastic, are described in comparison to those of poly(3-hexylthiophene) (P3HT, n = 6) and poly(3octylthiophene) (P3OT, n= 8). Neat P3HpT was found to have mechanical properties similar to that of P3 OT, and when mixed in 1:1 blends with the fullerene [6,6]-phenyl C-61 butyric acid methyl ester (PCBM), exhibited electronic properties comparable to P3 HI. However, the charge-carrier mobility of neat P3HpT is substantially inferior to that of P3HT; the good performance of P3HpT-based solar cells is the result of improved mobility in P3HpT:PCBM blends compared to the neat material. While P3HpT may be a favorable alternative to P31-IT in ultra-flexible, stretchable, and mechanically robust organic solar cells, P3HpT would only make a good field-effect transistor in situations in which mechanical compliance was more important than high mobility. (C) 2015 Elsevier B.V. All rights reserved.