A series of narrow-band gap conjugated molecules with specific fluorine substitution patterns has been synthesized in order to study the effect of fluorination on bulk thermal stability. As the number of fluorine substituents on the backbone increase, one finds more thermally robust bulk structures both under inert and ambient conditions as well as an increase in phase transition temperatures in the solid state. When integrated into field-effect transistor devices, the molecule with the highest degree of fluorination shows a hole mobility of 0.15 cm(2)/V.s and a device thermal stability of >300 degrees C. Generally, the enhancement in thermal robustness of bulk organization and device performance correlates with the level of C-H for C-F substitution. These findings are relevant for the design of molecular semiconductors that can be introduced into optoelectronic devices to be operated under a wide range of conditions.