Sugar phosphates provide metal-binding sites both at their sugar core and at their phosphate group(s). Mixed sugar-core-phosphate chelation has been considered as a typical bonding mode within the physiological pH range for the central metabolite D-fructose 1,6-bisphosphate. The Re(V)O(tmen) metal fragment was used to enrich this coordination type. The formation of the [ReO(tmen)(Fruf2,3H-21,6P2H2-κ(3)O(2,3,P1))](-) monoanion was determined by NMR spectroscopy and mass spectrometry. The model compound rac-glycerol 1-phosphate yielded similar results in terms of NMR spectroscopy. Crystal-structure analyses of [ReO(tmen)(rac-Glyc2,3H-21PH-κ(3)O(2,3,P))]·2H2O and [ReO(phen)(rac-Glyc2,3H-21PH-κ(3)O(2,3,P))]·MeOH confirmed the coordination pattern.