Stabilization of chromium(V) by biological 1,2-diolato ligands, e.g., carbohydrates and glycoproteins, is postulated to be crucial for both the chromium(VI)-induced carcinogenicity and chromium(III) antidiabetic activities. Close structural mimics of biologically relevant chromium (V) 1,2-diolato complexes, M[(CrO)-O-V(chd)(2)] [chd = cis-1,2-cyclohexanediolato(2-)], were synthesized and characterized by X-ray crystallography (M = Na) or by spectroscopic techniques, including X-ray absorption spectroscopy (M = K). This is the first structurally characterized chromium(V) complex with a cyclic diolato ligand.