The aromaticity and electronic properties of acetylene-bridged hexadehydrotristhiopheno[12]­annulenes (HDTAs) were revisited using a combined experimental and theoretical approach. Moreover, we attempted the synthesis of the butadiyne-bridged octadehydrobisthiopheno[12]­annulenes (ODTAs). While the formation of ODTAs was indicated by NMR spectroscopy, mass spectrometry, and UV–vis absorption measurements, our attempts to isolate ODTAs were unsuccessful on account of its instability. Instead, their structure and energetic properties were predicted using DFT calculations. HDTA isomers in which the position where the thiophene rings are fused to the 12-membered ring differs (b- vs c-position) show distinct differences in their HOMO–LUMO energy gaps (E Gap). ODTAs also show large E Gap differences depending on the fusion position of the thiophene rings. The diene character of the thiophene ring significantly changes the electronic properties; i.e., E Gap differences of >1 eV were observed between the isomers of both HDTAs and ODTAs. A theoretical evaluation of HDTAs and ODTAs revealed significant variation in the local aromaticity/antiaromaticity between the b- and c-isomers. The antiaromatic character of the 12-membered ring is attenuated for the b-isomers, whereas it is decreased substantially for the c-isomers. The results of this study are useful for a detailed understanding of the fundamental aspects of dehydrothiopheno[12]­annulenes.