Various core-modified tellurophene-containing pentaphyrin(2.1.1.1.1)s were synthesized via (3 + 2) condensation of 16-telluratripyrrane with different heterodiols under mild acid catalyzed conditions in 5-12% yields. The formation of pentaphyrin (2.1.1.1.1) with a N2O2Te core was not successful due to its inherent instability. The new pentaphyrins were characterized and studied by HR-MS, 1D and 2D NMR, X-ray crystallography for one of the pentaphyrins, absorption and DFT/TD-DFT techniques. The NMR studies indicated their nonaromatic nature. The X-ray structure obtained for pentaphyrin(2.1.1.1.1) with N4Te core revealed that the macrocycle exists in a highly distorted nonplanar structure. The DFT studies showed that the macrocycles are nonaromatic and exists in highly distorted nonplanar geometry. Furthermore, as the core heterocyclic groups at ethene moiety were changed from pyrrole to furan to thiophene to benzene, the macrocycles tended toward more planar structures. The absorption spectra of pentaphyrins showed one strong sharp band in the region of 450-540 nm along with a broad band in the region of 700-800 nm. The pentaphyrin(2.1.1.1.1) with N4Te core upon protonation showed distinct color change in solution and large bathochromic shifts in absorption bands with an absorption in the NIR region.