We report eight new A(2)B-type (Mn+) corrolate compounds (two structural studies) that include the oxo[5,15bis(pentafluorophenyl)-10-R-corrolatochromium(V)] [R = 2-/3-thienyl (1a/2a), 3-thianaphthyl (3a)] species. The first examples of meso-A(2) (thienyl)- and Cr-A(2)B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D (H-1 and C-13) NMR, and UV-vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu2+center dot center dot center dot O=Cr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A(2)B-corroles exhibited limited Mn+ selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh3 O-atom uptake from [O=Cr(cor)] was also demonstrated.