Empirical formulae, based upon thermo-analytical investigations, have been assigned for different cerium(IV) antimonate samples prepared under varying conditions of precipitation. Equilibria and apparent Na+-capacity measurements at different pH values were carried out to throw more light on their sorption behavior. From the general curve shape analysis of the capacity-pH curves, the possible ion exchange site acidity and site group concentration were characterized. The samples showed almost bifunctional cation exchange behavior. The results obtained are discussed in detail referring to some conclusions.