The objective of this study is to gain an understanding of the kinetics of adsorption of complexes formed in aqueous solution by oppositely charged polyelectrolytes. The properties of the complexes were characterized by means of dynamic light scattering and electrophoretic mobility and the reaction stoichiometry was studied by titration. The stoichiometry in the complexes depends on the polymer weight ratio w(p). Their point of zero charge (pzc) is shifted toward lower w(p) when simple cations of higher valence are added to the solution. The adsorption kinetics of the complexes on silica was studied by stagnation point reflectometry. The sign of charge of the complexes as well as the valence and concentration of simple cations governs the occurrence of adsorption in the electrolytes studied. Five different types of adsorption kinetics were found,