Uptake of calcium from food depends on solubility of calcium salts in the intestines, and precipitation of calcium phosphates decreases bioaccessibility of food calcium. Citrate as a high affinity complex binder for calcium was found spontaneously to create strongly supersaturated solutions by rapid dissolution of calcium hydrogen phosphate characterized by short lag phases for precipitation. Gluconate with weaker affinity for calcium binding showed longer lag phases for precipitation from supersaturated solutions. For citrate/gluconate combinations, the highest degree of supersaturation with longest lag phases for precipitation were found by trial-and-error experiments for a citrate/gluconate ratio of 1:10 for dissolution of calcium hydrogen phosphate resulting in supersaturation factors around three and without precipitation for more than a month. The aim of the present study was to provide a physicochemical explanation of this robust supersaturation. Calcium speciation based on electrochemical calcium activity measurement identified a low [Ca²⁺]·[HCitr²⁻] product as critical for supersaturation.