A series of hetero analogues of pentaphyrins(2.1.1.1.1) such as oxapentaphyrins(2.1.1.1.1) and thiapentaphyrins(2.1.1.1.1) were synthesized by 3 + 2 condensation of dipyrroethenedicarbinol with 16-oxatripyrrane/16-thiatripyrrane under mild acid-catalyzed reaction conditions. The stable macro- cycles are freely soluble in organic solvents, and their identities were confirmed by a corresponding molecular-ion peak in high-resolution mass spectrometry, 1D and 2D NMR spectroscopy, and X-ray structure obtained for one of the oxapentaphyrin(2.1.1.1.1) macrocycles. The crystal structure and NMR studies indicated that the heterocyclic ring, such as furan in oxapentaphyrins(2.1.1.1.1) and thiophene in thiapentaphyrins(2.1.1.1.1), was inverted. In absorption spectra, the macrocycles showed one sharp band at similar to 516 nm and one broad band at similar to 744 nm. The spectral and X-ray studies supported the nonaromatic nature of these macrocycles. This is in contrast to the recently reported aza analogue of pentaphyrins(2.1.1.1.1), which showed antiaromatic behavior. Upon protonation, the core-modified pentaphyrins(2.1.1.1.1) macrocycles exhibited bathochromically shifted absorption bands with a distinct change in the color of the solution. The NMR, nucleus-independent chemical shift, and anisotropy-induced current density studies indicated the presence of Mobius aromaticity in the protonated macrocycles. The core-modified pentaphyrins(2.1.1.1.1) can act as good coordinating ligands, as shown here by synthesizing a bis(difluoroborane) complex of one of the thiapentaphyrins(2.1.1.1.1).