We describe facial and meridional isomers of [Rh-III(pyalk)(3)], as well as meridional [Rh-IV(pyalk)(3)](+) {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh-III/IV redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV-visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.