The interfacial properties of a mixed system of low-charged cationic polyelectrolyte and silica nanoparticles has been studied by means of ellipsometry. Special attention was devoted to the effect that the order of addition of the two components has on the adsorption behavior of the mixed system. Adsorption on silica was in one case studied after simultaneous addition of the components to the aqueous solution. The measured adsorption rates were then much slower than expected for a mass-transfer limited process. This behavior signifies the presence of an electrosteric barrier arising due to preadsorbed polymer-particle complexes. Interfacial layers containing particles were at plateau conditions shown to be highly swollen, whereas the cationic polymer in the particle-free systems adopted a more flat surface conformation. The layer thickness was observed to monotonously increase with an increasing presence of nanoparticles in solution, while the surface excess showed a maximum at intermediate values. The finding was rationalized by the competition between particles and the surface for polymer charges leading to swelling and a decreased effective interaction between polymer and surface. In the other case studied, when polyelectrolyte and nanoparticles were added sequentially, a much more rapid concentration-dependent adsorption was observed. The kinetic adsorption barrier for nonassociated particles was clearly negligible compared with that for the polymer-particle complex. The surface excess did not exhibit an adsorption maximum as a function of added nanoparticles in this situation, indicating that the polymer layer to some degree is irreversibly anchored at the silica surface. Some implications of the above findings for practical papermaking using multicomponent retention systems are put forward.