The new fluorocarbon-functionalized polythiophenes, in particular, &agr;,&ohgr;-diperfluorohexylsexithiophene DFH-6T (1) can be straightforwardly prepared in high yield and purified by gradient sublimation. Introduction of perfluorocarbon chains on the thiophene core affords enhanced thermal stability and volatility, and increased electron affinity versus the fluorine-free analog 2. Evaporated films of 1, for example, behave as n-type semiconductors, and can be used to fabricate thin film transistors with FET mobilities on the order of ˜0.01 cm2/Vs—some of the highest reported to date for n-type organic semiconductors.