Inkjet ink colorants usually require different substrate modification depending on the colorant chemistry, solvent composition, and ink formulation. In this work, the authors investigated a novel concept based on alternating layers of anionic and cationic polyelectrolytes on a paper surface and the impact on ink colorant fixing and liquid absorption. The effect of nanoparticles in polyelectrolyte layers was investigated in order to clarify the changes in absorption rates. The alternating layering of micron-thin layers of cationic and anionic polyelectrolytes subjected to interim drying showed that the spreading and absorption of nanosize pigmented water-based ink were sensitive to the charge characteristics of the polyelectrolyte multilayer and also to the presence of nanopigments that enhanced the absorption speed and capacity. The interlayer polyelectrolyte complexing resulted not only in different ink-trapping fixing effects, but also in varying uniformity in ink spreading and absorption.