The adsorption behavior of highly charged cationic polyelectrolytes onto porous substrates is electrostatic in nature and has been shown to be highly dependent on the poly electrolyte properties. Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC) were synthesized to have a range of macromolecular properties (i.e., charge density and molecular mass). Traditional titration methods have been complemented by fluorescence labeling techniques that were developed to directly observe the extent that fluorescently labeled poly(AM-co-DADMAC) adsorbs into the pore structure of a cellulosic substrate. Although contributing to the electrostatic driving force, the charge density acts to limit adsorption to the outermost surface under electrolyte-free conditions. However, adsorption into the pores can occur if both the molecular mass and charge density of poly(AM-co-DADMAC) are sufficiently low. Adsorption initially increases as the electrolyte concentration is increased. However, the electrostatic persistence length of poly(AM-co-DADMAC) restricts the polyelectrolyte from entering the pores. Therefore, changes in the adsorption behavior at moderate electrolyte concentrations have been attributed to swelling of the polyelectrolyte layer at the fiber exterior. The adsorption behavior changes again at high electrolyte concentrations such that poly(AMco-DADMAC) could adsorb into the pore structure. This occurred when the electrolyte concentration was sufficient to screen the electrostatic persistence length of poly(AM-co-DADMAC), provided that the entropie driving force for adsorption still existed. It is suggested that adsorption into the pore structure is a kinetic process that is governed by localized electrostatic interactions between poly(AM-co-DADMAC) and the charges located within the pores.