Mechanisms of inkjet ink spreading and absorption on a coated paper have been studied using a polyelectrolyte multilayering technique. By applying alternating sequences of cationic and anionic polyelectrolyte layers on a mineral coated paper, the role of the interfacial chemistry was evaluated. The polyelectrolyte multilayer was created to imitate a thin resin-like liquid-absorptive layer and to clarify the role of the charge of the protruding polyelectrolyte layer on ink spreading and colorant fixation. The formation of a thin polyelectrolyte layer and coating coverage was confirmed by X-ray photoelectron spectroscopy (XPS). A submolecular mechanical imaging of the polyelectrolyte complexes with an atomic force microscope (AFM) revealed differences in modulus and different nanosize agglomerates were identified which were ascribed to polyion complexes. The polyelectrolyte coatings significantly affect the solid-liquid interaction and particularly the ink spreading revealed as intercolor bleeding and wicking. The interfacial interaction between the ink and the applied polyelectrolyte layers showed differences between dye- and pigment-based colorants, which could be emphasized by the polyelectrolyte chemistry. (C) 2014 Elsevier Inc. All rights reserved.