A series of electron-deficient π-conjugated systems with 4,9-dihydro-s-indaceno[2,1-d:6,5-d']dithiazole-4,9-dione-based structures and fluorinated acyl groups as the terminal units have been designed and synthesized for application as organic field-effect transistor (OFET) materials. The thermal, photophysical, and electrochemical properties and OFET performance of the synthesized compounds were investigated. OFET evaluation revealed that all compounds exhibited typical electron-transporting characteristics, and electron mobilities up to 0.26 cm(2) V(-1) s(-1) could be achieved. The air stabilities of OFET operation were dependent on the nature of the compounds and were investigated by X-ray diffraction and atomic force microscopy. The terminal units had a great influence not only on the molecular properties, but also on the film-forming properties and OFET performance.