Organic field-effect transistors (OFETs) based on oligothiophene-functionalized truxene derivatives have been fabricated for use as novel star-shaped organic semiconductors in solution-processible organic electronics. The electronic and optical properties of compounds 1–3, with increasing numbers of thiophene rings at each of the three branches, have been investigated using scanning electron microscopy (SEM), X-ray diffraction measurements, and ultraviolet–visible (UV-vis) and photoluminescence spectroscopies. The results show that with a stepwise increase of the thiophene rings at every branch, a transition from a polycrystalline to an amorphous state is observed. The characteristics of compounds 1, 2, and 3 used for OFETs exhibit a significant difference. The mobility depends greatly on the morphology in the solid state, and decreases in going from 1 to 3. Mobilities up to 1.03 × 10–3 cm2 V–1 s–1 and an on/off ratio of about 103 for compound 1 have been achieved; these are the highest values for star-shaped organic semiconductors used for OFETs so far. All the results demonstrate that the truxene core of the oligothiophene-functionalized truxene derivatives not only extends the π-delocalized system, but also leads to high mobilities for the compounds.