Organic semiconductors exhibiting complementary-type carrier mobility are the key components for the development of the field of “plastic electronics”. We present here a novel series of αω- and isomerically pure β,β'-diperfluorohexyl-substituted thiophene and study the impact of fluoroalkyl substitution and conjugation length vìs-à-vìs the corresponding fluorinefree analogues. Trends between the fluorinated and fluorine-free families in molecular packing, HOMO-LUMO gap, and π-π interactions are found to be strikingly similar. TFT measurements indicate that all members of the fluorinated series are n-type semiconductors