The previously reported pseudotetrahedral Co(I) complexes, CoX(PR(3))(3), where R = Me, Ph, and chelating analogues, and X = Cl, Br, I exhibit a spin triplet ground state, which is uncommon for Co(I), although expected for this geometry. Described here are studies using electronic absorption and high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy on two members of this class of complexes: CoX(PR(3))(3), where R = Ph and X = Cl and Br. In both cases, well-defined spectra corresponding to axial spin triplets were observed, with signals assignable to three distinct triplet species, and with perfectly axial zero-field splitting (zfs) given by the parameter D = +4.46, +5.52, +8.04 cm(-1), respectively, for CoCl(PPh(3))(3). The crystal structure reported for CoCl(PPh(3))(3) shows crystallographic 3-fold symmetry, but with three structurally distinct molecules per unit cell. Both of these facts thus correlate with the HFEPR data. The investigated complexes, along with a number of structurally characterized Co(I) trisphosphine analogues, were analyzed by quantum chemistry calculations (both density functional theory (DFT) and unrestricted Hartree-Fock (UHF) methods). These methods, along with ligand-field theory (LFT) analysis of CoCl(PPh(3))(3), give reasonable agreement with the salient features of the electronic structure of these complexes. A spin triplet ground state is strongly favored over a singlet state and a positive, axial D value is predicted, in agreement with experiment. Quantitative agreement between theory and experiment is less than ideal with LFT overestimating the zfs, while DFT underestimates these effects. Despite these shortcomings, this study demonstrates the ability of advanced paramagnetic resonance techniques, in combination with other experimental techniques, and with theory, to shed light on the electronic structure of an unusual transition metal ion, paramagnetic Co(I).