Inkjet printing was used to deposit alternating 100 nm layers of anionic and cationic polymers in order to form self-assembled ionic complexes on flat and fabric substrates. The layers formed are characterized by elemental analysis, microscopy and solubility. As initially deposited, layers are soluble but form insoluble complexes when they are heated and annealed. This approach has been applied to polypeptides, polymer dyes, polymers with nanoparticulate pigments, and hydrogels.