The effect of the structure of three-layer polyelectrolyte coatings on the interaction with a water-based inkjet ink comprising dye colorants was determined. Various combinations of anionic–cationic polyelectrolyte structures were prepared on base paper having different hydrophobicity obtained by varying dosages of an alkyl succinic anhydride (ASA) internal sizing agent. Thin coating layers of anionic NaCMC and/or cationic PDADMAC were alternately wet-on-wet spray-coated onto the substrates. It was found that the level of internal sizing affected the spreading and absorption of dye-based inkjet ink, but that the behavior was strongly dependent on the chemistry and structural composition of the deposited polyelectrolyte layer. Polyelectrolyte surface treatment had an effect on the print quality and, e.g., the print density could be improved with cationic surface treatment but also with increasing level of internal sizing. A significant difference in the water fastness of the printed samples was seen, which could be ascribed to the influence of complexes formed between anionic and cationic polyelectrolytes and to their interactions with ink colorants.