Nine different a,v-phenyl-endcapped bithiophenes were synthesised, and the effect of the different side chains on the liquid crystalline properties, alignment ability and charge carrier mobility have been studied. An increase in chain length leads to a decrease in the liquid crystalline–isotropic phase (clearing) transition temperature. Remarkably, introduction of an asymmetric carbon centre close to the p-conjugated segment resulted in the loss of the liquid crystalline phase. Alignment on rubbed polyimide was obtained for the liquid crystalline thiophene derivatives lacking heteroatoms in the side chain and for the chiral a,v-phenyl-endcapped bithiophene. Some bithiophenes showed bipolar charge transport in time-of-flight (TOF) measurements, with mobilities up to 3 6 1023 cm2 V21 s21 in the liquid crystalline state. Field effect transistors revealed mobility for holes up to 1 6 1023 cm2 V21 s21 (crystalline state). From the data set obtained, it can be concluded that the use of linear hydrocarbon chains as solubilising tails in these types of p-conjugated building blocks gives the best overall electronic performance.