Oxidation of dihydroxyhetero[7]helicenes gave dihetero[8]circulenes via the concomitant C-C coupling and dehydrative furan formation. The pristine dihetero[8]circulenes were synthesized in four steps and characterized for the first time. X-ray crystal structures and DFT-optimized structures revealed the distorted saddle-like structures, and the degree of the distortion was found to be correlated with the photophysical properties.