A series of V(III) complexes of varying coordination number (5, 6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L-n](0,-), where n = 1 (from L = Cl-, 1-Me-Im, N-3(-)), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N2H4). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S = 1 spill ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI), The zfs in these complexes is relatively small in magnitude (vertical bar D vertical bar approximate to 1 cm(-1)) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.