The adsorption of cationic starch (CS) from aqueous electrolyte solutions onto model cellulose film has been investigated by the quartz crystal microbalance with dissipation monitoring (QCM-D) and X-ray photoelectron spectroscopy (XPS). The influence of the electrolyte composition and charge density of CS was examined. The adsorption of CS onto cellulose followed the general trends expected for polyelectrolyte adsorption on oppositely charged surfaces, with some exceptions. Thus, as result of the very low surface charge density of the cellulose surface, highly charged CS did not adsorb in a flat conformation even at low ionic strength. The porosity of the film, however, enabled the penetration of coiled CS molecules into the film at high electrolyte concentrations. Differences between the adsorption behavior of CS on cellulose and earlier observations of the adsorption of the same starches on silica could be explained by the different morphologies and acidities of the hydroxyl groups on the two surfaces.