The chemical mechanism displayed in the sorption of heavy metal cations on barks was discussed through a modelling study of adsorption in relation to the nature of the ligand borne by the chemical components of the bark sorbent. The adsorption isotherms of five heavy metal cations (Cr3 +, Cu2 +, Ni2 +, Pb2 +, Zn2+) on five species of barks (Sweet chestnut, Oak, Douglas fir, Norway spruce, Scots pine species) were studied. The experimental data fitted well the Langmuir model, which allowed the expression of the mathematical parameters (qmax, maximum binding capacity; b, affinity). The qmax values increased conversely to the b values. The correlation of these mathematical values (qmax and b) with the analysis of the chemical composition of barks led us to note that Cu2 + interacts preferentially with phenolic groups present in lignins and tannins and, opposite in, Pb2 + with the carboxylic acid groups in polysaccharides. These observations were explained (i) quantitatively by the amount of different types of sites and (ii) qualitatively, by the physicochemical characteristics of cations, the nature and the tridimensional structure of adsorption sites. Finally, the results allowed to define the nature of the chemical interaction (monodentate or multidentate complex) between each specified chemical component of barks and each kind of heavy metal cations.