A postassembly acid-treatment consisting of an immersion in 5 mM HCl solution was applied to carboxylated cellulose nanofibrils (CNF)-poly(allylamine) hydrochloride (PAH) multilayered thin films. Our results show that the treatment did not affect the overall thickness of the films without any loss of the components. However, a modification of the surface morphology was observed, as well as the swelling behavior. The process was perfectly reversible since the original structure was recovered when the thin films were rinsed by ultrapure water. Moreover, a more pronounced antireflective character was detected for the treated films. The origin of these reversible modifications was discussed. Notably, the scattering length density (SLD) profiles of the films before and after treatment support the idea of a structural reorganization of the components within the film driven by the change of their charge densities induced by the acid treatment.