Synthetic protocols were developed for the gram-scale preparation of two isomeric dithienoborepins (DTBs), boron-containing polycyclic aromatics featuring the fusion of borepin and thiophene rings. DTBs exhibit reversible cathodic electrochemistry and boron-centered Lewis acidity in addition to enhanced electronic delocalization relative to benzo-fused analogues. Boron's precise position within the conjugation pathway of DTBs significantly affected electronic structure, most clearly demonstrated by the variation in spectroscopic responses of each isomer to fluoride ion binding. In addition to excellent stability in the presence of air and moisture, DTBs could also be subjected to electrophilic aromatic substitution and metalation chemistry, the latter enabling the direct, regiospecific functionalization of the unsubstituted thiophene rings. Subsequent tuning of molecular properties was achieved through installation of donor and acceptor pi-substituents, leading to compounds featuring multistep electrochemical reductions and polarizable electronic structures. As rare examples of directly functionalizable, pi-conjugated, boron-containing polycyclic aromatics, DTBs are promising building blocks for the next generation of organoboron pi-electron materials whose development will demand broad scope for molecular diversification in addition to chemical robustness.