Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co4O4(C5H5N)4(CH3CO2)4]+ (1+), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt phosphate (Co Pi) wateroxidizing catalyst. The Davies electron nuclear double resonance (ENDOR) spectrum is wellmodeled using a single class of hyperfine-coupled 59Co nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [ 20((2), 77((1), 5((15)] MHz). Mims 1HENDOR spectra of 1+ with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobaltbonding partner is significantly reduced from unity. Multifrequency 14N ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3dxz,yz-based molecular orbital for this essentially [Co+3.125 4O4] system. Comparing the EPR spectrum of 1+ with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst.