Continuing dissolution of solid calcium L-lactate pentahydrate in saturated aqueous solutions following addition of solid sodium D-gluconate corresponding to a gluconate/lactate ratio around three was found to result in homogeneous solutions supersaturated with calcium D-gluconate by a factor of seven, from which calcium D-gluconate monohydrate precipitated only slowly. In contrast, dissolution of calcium D-gluconate monohydrate by sodium L-lactate in aqueous solution with the reverse lactate/gluconate ratio also around three did not result in similar homogeneous solutions on the route to solid calcium L-lactate pentahydrate. This increasing supersaturation of calcium D-gluconate during dissolution of calcium L-lactate in aqueous sodium D-gluconate may enhance calcium bioavailability. The dissolution overshooting depends on competitive kinetics and is also of interest in modeling biomineralization and in designing novel food products with increased calcium bioavailability.