The synthesis and characterization of cofacial copper biscorroles and porphyrin-corroles linked by a biphenylenyl or anthracenyl spacer are described. The investigated compounds are represented as (BCA)Cu-2 and (BCB)Cu-2 in the case of the biscorrole (BC) derivatives and (PCA)Cu-2 and (PCB)Cu-2 in the case of porphyrin (P)-corrole (C) dyads, where A and B represent the anthracenyl and biphenylenyl bridges, respectively. A related monomeric corrole (Me4Ph5Cu)Cu and monomeric porphyrin (Me2Et6PhP)Cu that comprise the two halves of the porphyrin-corrole dyads were also studied. Electron spin resonance (ESR), H-1 NMR, and magnetic measurements data demonstrate that the copper corrole macrocycle, when linked to another copper corrole or copper(II) porphyrin, can be considered to be a Cu(III) complex in equilibrium with a Cu(II) radical species, copper(III) corrole being the main oxidation state of the corrole species at all temperatures. The cofacial orientation of (BCB)Cu-2, (BCA)Cu-2, and (PCB)Cu-2 was confirmed by X-ray crystallography. Structural data: (BCB)Cu-2(C(110)H(82)N(8)Cu(2)(.)3CDCl(3)), triclinic, space group P (1) over bar, a = 10.2550-(2) Angstrom, b = 16.3890(3) Angstrom, c = 29.7910(8) Angstrom, alpha = 74.792(1)degrees, beta 81.681 (1)degrees, gamma = 72.504(2)degrees, Z = 2; (BCA)Cu2-(C(112)H(84)N(8)Cu(2)(.)C(7)H(8)(.)1.5H(2)O), monoclinic, space group P2(1)/c, a 16.0870(4) Angstrom, b = 35.109(2) Angstrom, c = 19.1390(8) Angstrom, beta = 95.183(3)degrees, Z = 4; (PCB)Cu-2(C(89)H(71)N(8)Cu(2)(.)CHCl3), monoclinic, space group P2(1)/n, a = 16.7071(3) Angstrom, b = 10.6719(2) Angstrom, c = 40.8555(8) Angstrom, beta = 100.870(1)degrees, Z = 4. The two cofacial biscorroles, (BCA)Cu-2 and (BCB)Cu-2, both show three electrooxidations under the same solution conditions. The reduction of (BCA)Cu-2 involves a reversible electron addition to each macrocycle at the same potential of E-1/2 = -0.20 V although (BCB)Cu-2 is reversibly reduced in two steps to give first [(BCB)Cu-2](-) and then [(BCB)Cu-2](2-), each of which was characterized by ESR spectroscopy as containing a Cu(II) center. These latter electrode reactions occur at E-1/2 = -0.36 and -0.51 V versus a saturated calomel reference electrode. The half-reduced and fully reduced (BCB)Cu-2 show similar Cu(II) ESR spectra, and no evidence of a triplet signal is observed. The two well-separated reductions of (BCB)Cu-2 to give [(BCB)Cu-2](2-) can be attributed to a stronger pi-pi interaction between the two macrocycles of this dimer as compared to those of (BCA)Cu-2. The copper porphyrin-corrole dyads, (PCA)Cu-2 and (PCB)Cu-2, show five reversible oxidations and two reversible reductions, and these potentials are compared with corresponding values for electrochemical reactions of the porphyrin and corrole monomers under the same solution conditions.