Three examples of dibenzi heteroheptaphyrin(2.0.1.1.1.1.0)s were synthesized by condensing bis(phenylene ethene) based hexapyrrane with appropriate diol, 2,5-bis(α-hydroxy-α-arylmethyl) thiophene or selenophene in CH2 Cl2 under BF3 ⋅ OEt2 catalyzed inert atmosphere conditions followed by DDQ oxidation in open air. HR-MS analyses confirmed the identities of dibenzi heteroheptaphyrins. The DFT optimized structures revealed that dibenzi heteroheptaphyrins were highly distorted nonplanar macrocycles with two thiophene rings preferred to be in an inverted conformation. 1D & 2D NMR helped in deducing the molecular structures of dibenzi heteroheptaphyrins and supported their nonaromatic nature. The theoretical NMR calculations were carried which matched closely with the experimental NMR data. NMR studies also revealed that the π-delocaliztion was significantly altered in dibenzi heteroheptaphyrins compared to previously reported dibenzi hexaphyrins. The dibenzi heptaphyrins showed one sharp absorption band in 400-500 nm region and a broad band in the region of 600-800 nm which were bathochromically shifted in their diprotonated derivatives. The theoretical absorption calculations corroborate the slight hypsochromic shift of the broad absorption band in the lower energy region of dibenzi heptaphyrins compared to dibenzi hexaphyrins. The electrochemical studies revealed that the dibenzi heptaphyrins were easier to reduce but difficult to oxidize compared to dibenzi hexaphyrins.