Solution and solid-state properties of two new perfluoroalkyl end-substituted analogues of distyryl-bithiophene (CF3-DS2T and diCF(3)-DS2T) are presented. Vacuum deposited thin films were investigated by atomic force microscopy, X-ray diffraction, and implemented as active layers into organic thin film transistors. While physicochemical measurements in solution suggest a preferential hole injection and transport inside CF3-DS2T and diCF(3)-DS2T films, electrical measurements performed under high vacuum show that CF3-DS2T behaves as n-type semiconductor while no charge transport was measured in diCF(3)-DS2T. The results highlighted the importance of substituents on conjugated backbone and on the resulting fine ordering in solid state to control the charge transport. (C) 2012 Elsevier Ltd. All rights reserved.