Thiadiazoloquinoxaline-fused naphthalenediimides (TQ-f-NDIs) are designed and synthesized. They show high electron affinities (EAs) of ∼4.5 eV. Organic field-effect transistor (OFET) devices, fabricated by dip-coating, provided maximum high electron mobilities of 0.03 cm2/(V·s) with an on/off ratio of 2 × 105.