The magnetic susceptibilities in the temperature range 80–300°K and ultraviolet and visible spectra of sixteen hexaco-ordinated complexes of vanadium(III) have been measured. Spectral data are consistent with octahedral formulations. The magnetic data are compared with the theory for a 3T1g ground term perturbed by spin–orbit coupling, ligand field components of axial symmetry, and an orbital reduction factor. Values of the parameter A for a wide range of ligands are shown to be rather similar. The splitting of the ground term due to asymmetry of the ligand field varies from 150–300 cm.–1 for MX6 complexes to 500–1000 cm.–1 for complexes with dissimilar ligands or three bidentate ligands.