A series of 12 thieno-fused macrocycles based on the dehydro [14] annulene framework have been prepared. Studies have focused on the optical and electronic properties of the dehydrobenzothieno [14] annulenes (DBTAs) and dehydrothieno [14] annulenes (DTAs) utilizing NMR spectroscopy, UV− vis spectrophotometry, electrochemistry, and DFT computations. X-ray crystal structures were also obtained for two of the macrocycles. The ...