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^VO(tmen) metal fragment was used to enrich this coordination type. The formation of the [ReO(tmen)(Fruf2,3H₋₂1,6P₂H₂-κ³O^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-κ³O^2,3,P)]·2H₂O and [ReO(phen)(rac-Glyc2,3H₋₂1PH-κ³O^2,3,P)]·MeOH confirmed the coordination pattern.