Contrary to suggestions in the literature, it has been proven that Al(III) forms a 1 : 1 complex with gluconate (hereafter Gluc⁻) in strongly alkaline (pH > 12) aqueous solutions. The complex formation was proven via²⁷Al and ¹H NMR, freezing-point depression, polarimetric measurements as well as potentiometric and conductometric titrations. This complexation is a pH independent process, i.e., a condensation reaction takes place. The stability constant of the complex formed was derived from ¹H NMR and polarimetric measurements, and was found to be log K = 2.4 ± 0.4. In the complex formed, Al(III) has a tetrahedral geometry, and the Al(OH)₄⁻ is most probably statistically distributed between the alcoholate groups of the Gluc⁻.