The synthesis of a novel 3,3'-difluoro-4,4'-dihexadecyl-2,2'-bithiophene monomer and its copolymerisation with thieno[3,2-b]thiophene to afford the fluorinated analogue of the well-known poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]-thiophene) (PBTTT) polymer is reported. Fluorination is found to have a significant influence on the physical properties of the polymer, enhancing aggregation in solution and increasing melting point by over 100 °C compared to non-fluorinated polymer. On the basis of DFT calculations these observations are attributed to inter- and intra-molecular S…F interactions. As a consequence, the fluorinated polymer PFBTTT exhibits a four-fold increase in charge carrier mobility compared to the non-fluorinated polymer and excellent ambient stability for a non-encapsulated transistor device.