The tris‐glycinatochromium(III) complex ([Cr(gly)3]) has been proposed as a nutritional supplement and treatment for Type 2 diabetes. The exact mode of action of this and other Cr(III) supplements is not known but may involve redox reactions with biomolecules. In this study fac‐[Cr(gly)3] was synthesized and the electrochemical properties investigated by cyclic voltammetry. The complex undergoes a reversible one electron reduction with E1/2=−0.66 to −0.69 V that is essentially independent of scan rate. Thermal decomposition was explored by differential scanning calorimetry under nonisothermal conditions from 30−1000 °C. Structural parameters obtained from DFT calculations are in good agreement with crystallographic data. The reduced form of the complex has a high‐spin quintet electronic configuration due to the small crystal field splitting from the weak π‐donor ligands. Both the theoretical calculations and the electrochemical measurements demonstrate that the complex is stable in the anionic form. These results indicate that [Cr(gly)3] can undergo reversible electron transfer, which may play a role in it's biological activity.