Oxidative dimerization of pi-conjugated molecules is a straightforward approach for effectively extending pi-conjugation and absorption features. However, it is challenging to construct dimeric species of bulky pi-conjugated frameworks because of the steric hindrances and/or poor regioselectivity. To address these issues, a pyrrole unit has been regioselectively appended to the alpha position of N-confused hexaphyrin (1.1.1.1.1.0) 1 by a facile acid-catalyzed condensation reaction, leading to the formation of pyrrole-appendant 2. Subsequent oxidation of 2 yielded an inner-fused monomer 2F and two fused dimeric species, namely, (2F) 2 a and (2F) 2 b. In contrast, oxidation of the corresponding Ni(II) complex 2Ni generated dimer (2Ni) 2 . Subsequent demetalation resulted in the formation of bipyrrole-linked freebase dimer (2) 2 , which could chelate Ni(II) and Cu(II) ions to furnish complexes (2Ni) 2 and (2Cu) 2 , respectively. In comparison to the fused dimeric species (2F) 2 a and (2F) 2 b, the nonfused dimer (2) 2 and its complexes (2Ni) 2 and (2Cu) 2 exhibit diminished local aromaticity, narrowed HOMO-LUMO gaps, and a red-shifted absorption profile that extends up to 2200 nm. These findings underscore a potent strategy for creating expanded porphyrin dimers, wherein the aromaticity and near-infrared absorption can be fine-tuned by incorporating an appendant pyrrole unit.