137Cs extraction experiments were performed on 14 contaminated soils from NW Italy with different characteristics and mineralogical composition. Solutions of HCl (pH = 0.5) and buffered EDTA/ammonium acetate (Lakanen solution) were used to assess bioavailability. The results show that less than 2% of 137Cs is available for leaching and/or root uptake. Even within a complex natural system it was possible to identify the amount of swelling clays (vermiculite + smectite) as the main control on Cs mobility under acidic conditions. The ammonium ion appears to be effective in desorbing Cs and its role is briefly discussed in terms of crystal chemistry. The relevance of mineralogy in assessing soil vulnerability is underlined.