Polymer nanocapsules assembled on cationic liposomes have been built through the layer-by-layer (LbL) technique. Chitosan and alginate, two biocompatible polyelectrolytes, were used to cover the template, where the Rhodamine B was previously loaded. The multishell formed with the alternate deposition of the polyelectrolytes, according to the principles of the LbL assembly, was supposed to change the permeability of the capsule wall. The thickness of the multishell was seen increasing with the number of layers deposited through the observations with the Transmission Electron Microscope. The permeability of the capsules was studied through Rhodamine B release assays. Nanocapsules with seven layers of polyelectrolytes released the dye slowly compared to the capsules with three or five layers. The Ritger-Peppas model was applied to investigate the release mechanisms and a non-Fickian transport behavior was detected regardless of the number of layers. Values of diffusion coefficients of Rhodamine B through the capsule wall were also calculated.