Three new fused-ring pyrazine derivatives end-functionalized with trifluoromethylphenyl groups have been synthesized. The effect of a fused-ring pyrazine core on the thermal, electronic, optical, thin film morphology, and organic field-effect transistor (OFET) properties was investigated both experimentally and theoretically. Electrochemistry measurements and density functional theory calculations suggest that the pyrazine core plays a significant role in tuning the electron affinities of these compounds. The optical absorption and fluorescence properties are also sensitive to the pyrazine core. The OFET devices based on the fused-ring pyrazine compounds exhibit electron mobilities as high as ca. 0.03 cm(2) V(-1) s(-1) under nitrogen, and their performance is sensitive to the pyrazine core. The larger pyrazine core leads to a lower LUMO level and lower reorganization energy, to more ordered thin film morphology with larger grain size, and finally to higher mobilities.