Three types of alkylated peri-xanthenoxanthene (PXX) have been synthesized employing efficient synthetic routes. These heteroaromatic compounds exhibited different electronic and crystal structures according to UV-vis spectra, electrochemical measurements, and X-ray structural analyses. Among them, 1,7-DOPXX has been demonstrated as an active material for organic field-effect transistors with promising mobility and a high on/off ratio simultaneously.