We have synthesized three PPEGMEMA-based cationic copolymers with similar amine contents but with systematic variation in the average length of the PEG side chains. The positively charged copolymers were paired with alginate to fabricate layer-by-layer assembled multilayered films. It was demonstrated that the polymeric design, in terms of the systematic variation in the average length of the PEG units, affects the polyelectrolyte multilayer growth mechanism and can be used to tune the structural properties and the water content of the layers. In addition, by partial cross-linking of the amine groups present in the copolymer backbone, disintegration of the film induced by pH changes was prevented. Finally, it was demonstrated how the cross-linked multilayered film can exhibit cationic, zwitterionic and anionic properties depending on the pH value and how these changes are associated with swelling, layer contraction and changes in water content.