Three copper dibenzoporphyrin(2.1.2.1) complexes having two dipyrromethene units connected through o-phenylen bridges and 4-MePh, Ph, or F5Ph substituents at the meso positions of the dipyrrins were synthesized and characterized according to their spectral, electrochemical, and structural properties. As indicated by the single-crystal X-ray structures, all three derivatives have highly bent molecular structures, with angles between each planar dipyrrin unit ranging from 89° to 85°, indicative of a nonaromatic molecule. The insertion of copper(II) into dibenzoporphyrins(2.1.2.1) induced a change in the macrocyclic cavity shape from rectangular in the case of the free-base precursors to approximately square for the metalated copper derivatives. Solution electron paramagnetic resonance (EPR) spectra at 100 K showed hyperfine coupling of the Cu(II) central metal ion and the N nucleus in the highly bent molecular structures. Electrochemical measurements in CH2Cl2 or N,N-dimethylformamide (DMF) containing 0.1 M tetrabutylammonium perchlorate (TBAP) were consistent with ring-centered electron transfers and, in the case of reduction, were assigned to electron additions involving two equivalent π centers on the bent nonaromatic molecule. The potential separation between the two reversible one-electron reductions ranged from 230 to 400 mV in DMF, indicating a moderate-to-strong interaction between the equivalent redox-active dipyrrin units of the dibenzoporphyrins(2.1.2.1). The experimentally measured highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps ranged from 2.14 to 2.04 eV and were smaller than those seen for the planar copper tetraarylporphyrins(1.1.1.1), (Ar)4PCu.