The preparation and characterization of two π-cation radical derivatives of copper β-oxo porphyrins is described. [3,3,8,8,13,13,17,18-Octaethyl-(3H,8H,13H)-porphine-2,7,12-trionato (2-)] copper π-cation radical, [Cu(2,7,12-trioxoOEHP(.))](+), and [3,3,8,8,12,13,17,18-octaethyl-(3H,8H)-porphine-2,7-dionato(2-)] copper π-cation radical, [Cu(2,7-dioxoOEiBC(.))](+), have been prepared and characterized by single-crystal X-ray determinations, UV/vis/NIR, and IR spectroscopies. Both molecules have modest distortion from the planarity and show monomeric units in the solid state. [Cu(2,7-dioxoOEiBC(.))](+) shows a concentration dependent near-IR band at 1410 nm. Crystal data for [Cu(2,7,12-trioxoOEHP(.))][SbCl(6)]: tetragonal, space group P4(2)/n, a = 31.085 (14) Å, c = 9.410 (4) Å, V = 9093 Å(3), Z = 8, T = 127 K. Crystal data for [Cu(2,7-dioxoOEiBC(.))][SbCl(6)]: monoclinic, space group P2(1)/n, a = 9.655 (4) Å, b = 20.592 (8) Å, c = 43.347 (17) Åβ = 89.97(1)(°), V = 8618. Å(3), Z = 8, T = 100 K.