Five-coordinate Zn-II, Ni-II, and Cu-II complexes containing pentadentate N3O2 Schiff base ligands [1A](2-) and [1B](2-) have been synthesized and characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, two phenolate O-donors, and a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that the N3O2 coordination spheres of [Cu(1A)] and [Cu(1B)] are retained in CH2Cl2 solution and solid-state superconducting quantum interference device (SQUID) magnetometric studies confirm that [Ni(1A)] and [Ni(1B)] adopt high spin (S = 1) configurations. Each complex exhibits two reversible oxidation processes between +0.05 and +0.64 V vs [Fc](+)/[Fc]. The products of one- and two-electron oxidations have been studied by UV/vis spectroelectrochemistry and by EPR spectroscopy which confirm that each oxidation process for the Zn-II and Cu-II complexes is ligand-based with sequential formation of mono- and bis-phenoxyl radical species. In contrast, the one-electron oxidation of the Ni-II complexes generates Ni-III products. This assignment is supported by spectroelectrochemical and EPR spectroscopic studies, density functional theory (DFT) calculations, and the single crystal X-ray structure of [Ni(1A)][BF4] which contains Ni in a five-coordinate distorted trigonal bipyramidal geometry.