The complex formation between metal ions and carbohydrates in solvent mixtures has been studied by chromatographic measurements. The effect of noncomplexing partition was decreased by attaching the active groups only on the shell of the stationary phase particles. Poly(styrene- co -divinylbenzene) resin beads were surface-sulfonated for that purpose. Thus the inner part of the sulfonated bead remained inactive and nonswellable. The counter-ions examined were Na+ , Ca2+, and La3+, and the organic cosolvents were ethanol and acetonitrile. The stability constants of the very weakly complexing D-glucose, D-xylose, and L-rhamnose, the weakly complexing D-fructose and L-arabinose, and the strongly complexing xylitol and D-sorbitol were determined. The increasing organic cosolvent content increased the retention times, which is explained by the increased complex stability between the complexing solute and the counter-ion. The effect was greatest for the complex-forming sugars in the Ca2+ form and for the sugar alcohols in the La3+ form. The organic cosolvent had only a minor effect on the weakly complexing components, whereas the complex stability of the strongly complexing xylitol and sorbitol in 50 wt% ethanol solution in the La3+ resin was more than five times higher compared to the stability measured in pure water.