The adsorption of HSA onto CHI/ALG multilayer assemblies was assessed in situ using QCM‐D. It was found that the behavior of HSA on biomaterials surface can be tuned by adjusting parameters of the polyelectrolyte system such as pH, layer number, crosslinker and polymer terminal layer. Our results confirmed the key role of electrostatic interactions during HSA adsorption, since oppositely charged surfaces were more effective in promoting protein adhesion. QCM‐D data revealed that crosslinking (CHI/ALG)5CHI films allows HSA to become adsorbed in physiological conditions. Our results suggested that the biological potential of biopolymers and the mild conditions of the LbL technique turn these natural nanoassemblies into a suitable choice to be used as pH‐sensitive coatings.