The understanding of the availability of a metal in soil necessitates a minimum knowledge about its speciation in the soil solution. Here, we evaluated an alternative to the use of ion exchangers for estimating the free ionic fraction of cadmium (F-Cd) in solution. It is based on the exchange selectivity coefficient (K-V) rather than the distribution coefficient (K-D) to estimate F-Cd. Because K-V for the Cd-Ca exchange for the used Amberlite resin was independent of the solution Ca concentration (0.5-7.5 mM) and pH (range: 4.5-6), the experiment on a solution mimicking the analyzed solution to estimate K-V was not necessary. The influence of variable Ca and Mg concentrations in solution on F-Cd was assessed in synthetic solutions containing either citrate or malate. The best way to estimate Fe, seemed to treat the exchange data as if Ca was solely present. However, neither the proposed approach nor those applying K-D prevent the overestimation of FCd when Ca is partly complexed in the analyzed solution. A method intending to estimate two replicates of FCd for a given, unique solution was also studied on solutions issued from sorption-desorption experiments performed on a humic podzol. It consists of two successive supplies of a known resin mass to a unique sample. Both estimates were close and not significantly different.