Maximizing the functionality of cationic polydiallyldimethylammonium chloride (poly-DADMAC) additive with minimal dosage in inkjet coatings can contribute to both an improvement in quality and a cost reduction. To do this, it is essential to understand how the cationic additive is distributed in the coating layer and how it affects the print quality. This study presents a three-step investigation to enhance the understanding of the distribution of poly-DADMAC, as well as its effect on inkjet print quality. First, the adsorption behavior of poly-DADMAC on silica pigments was investigated by measuring the surface charge of silica and the adsorption of the cationic additive. Second, the influence of poly-DADMAC on the printability of binder films was investigated. Finally, the effect of poly-DADMAC on the print quality of inkjet paper was examined. The addition of poly-DADMAC improved the print quality of the inkjet paper because of the improved holdout of the negatively charged colorants in the ink.