A novel family of bisbenzothieno[b]-fused BODIPYs containing seven fused aromatic rings has been developed from readily available benzothieo[3,2-b]pyrroles through an efficient two-step synthetic route, exhibiting planar skeletons with excellent photostabilities, deep-red absorptions, and near-infrared emissions (up to 753 nm). Importantly, the thin-film transistors based on BTB with a meso-dimethylamino-phenyl group exhibit unipolar n-type charge transporting characteristics with a high electron mobility of 0.013 cm2 V-1 s-1.