We synthesize three liquid crystal molecules with angular anthradithiophene (a-ADT) as the core for the application in organic film-effect transistors (OFETs). Thiophene-octyl group and thiophene-dodecyl group are introduced on both sides of the a-ADT core to yield compounds Bis-C8T-a-ADT and Bis-C12T-a-ADT. Moreover, thiophene-dodecyl group is attached to the a-ADT core on one side to yield compound C12T-a-ADT. The synthesized compounds are measured by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) to determine their mesomorphic properties. Compound Bis-C8T-a-ADT shows nematic and smectic A phases while both compounds Bis-C12T-a-ADT and C12T-a-ADT reveal smectic A phases. The optical and electrochemical properties of the compounds are characterized by UV–vis spectroscopy and cyclic voltammetry (CV). The HOMO levels for Bis-C8T-a-ADT and Bis-C12T-a-ADT are estimated to be −5.27 eV while the HOMO level of C12T-a-ADT is estimated to be −5.34 eV. The low-lying HOMO levels of the molecules indicate their great oxidation stability in OFET devices. The carrier mobilities are observed to increase 10–1000 times using rubbed polyimide (PI), resulting from the better arrangements of the liquid crystal molecules, and excellent carrier mobilities of 1.06 and 1.02 cm2/Vs are obtained from compounds Bis-C12T-a-ADT and C12T-a-ADT, respectively.