The binding of 4 s-triazines herbicides and metabolites, ameline, hydroxyatrazine, atraton, and ametryn to 12 structurally different humic substances was studied by affinity capillary electrophoresis. Binding data were confronted to the structural data of humic acids obtained from spectrometric measurements (UV-Vis, FT/IR, NMR), elemental analysis and potentiometric titration. The results obtained with principal component analysis and partial least square analysis clearly show the importance of carboxylic acidity and aromaticity of the humic ligands in relation to the partial positive charge and relative hydrophobicity of the pesticides.