The behaviour of plutonium with respect to its migration in the aquifer has been studied under conditions close to nature. Most relevant under these conditions are Pu(III) and Pu(IV) in contact with humic substances (HS) and minerals. As a model for the host rock, kaolinite (KGa-1b) was chosen. The complexation of Pu(III) and Pu(IV) with Aldrich humic acid (AHA) in aqueous solution at ionic strength 0.1 M was investigated by the ultrafiltration method. The sorption of Pu(III) and Am(III) onto kaolinite (K) as a function of pH and metal-ion concentration was studied under aerobic and anaerobic conditions. The pH edge was found at pH∼5.5 independent of the metal-ion concentration and working atmosphere. The influence of HS on the sorption of Pu(III) and Pu(IV) onto kaolinite was investigated in the ternary systems Pu(III)-K-HS and Pu(IV)-K-HS and for comparison, in the system Th(IV)-K-HS. The dependence on pH, contact time, concentration of HS (for Pu(IV)-K-HS) was studied as well as the sequence in which the components were added. Generally, it was found that HS tend to enhance the sorption onto kaolinite below pH 6 and to decrease sorption at higher pH depending in detail on the sequence in which the components were added. An identification of the species sorbed on the surface of the kaolinite by X-ray absorption spectroscopy, as well as chemically, was attempted and preliminary results are discussed.