In this study, self-cross-linked chitosan/alginate dialdehyde multilayer films, capped with either alginate dialdehyde (6 layers) or chitosan (7 layers), were fabricated using the layer-by-layer method. The disruption of the electrostatic equilibrium when exposing the fabricated layers to acidic and alkaline conditions causes swelling within the film and independently in the outermost layer, showing dependence on the ionic strength. Spectroscopic ellipsometry and quartz crystal microbalance with dissipation monitoring were employed to examine the swelling behavior. Atomic force microscopy colloidal probe measurements were conducted to assess the surface forces between the multilayer films at different pH and ionic strengths. Finally, the electrostatic properties of the multilayer films were examined at different pH and ionic strengths using zeta potential measurements. The results suggest that stimuli-responsiveness and overall swelling behavior of the polysaccharide multilayer films significantly depend on the outermost layer, an effect that should expectedly become more pronounced the thinner the film becomes.