Two isomeric 1,4‐thiaborin derivatives fused by two thiophene rings (dithieno‐1,4‐thiaborins, DTTBs) were synthesized in two steps from commercially available materials, and their structures were confirmed by X‐ray crystallographic analysis. DTTBs 1 and 2 showed excellent stability towards air and moisture. Theoretical calculations revealed that the fusion of thiophenes enhanced the aromaticity of the centered 1,4‐thiaborins compared to their corresponding dibenzothiaborins. Furthermore, DTTBs 1 and 2 could be further functionalized by metalation followed by addition of electrophile. DTTBs are promising platforms upon which it is possible to build the next generation of organoboron π‐electron materials.

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