Model layer-by-layer (LbL) assemblies of poly(allylamine hydrochloride) (PAH) and hyaluronic acid (HA) were fabricated in order to study their wet adhesive behavior. The film characteristics were investigated to understand the inherent structures during the assembly process. Subsequently, the adhesion of these systems was evaluated to understand the correlation between the structure of the film and the energy required to separate these LbL assemblies. We describe how the conditions of the LbL fabrication can be utilized to control the adhesion between films. The characteristics of the film formation are examined in the absence and presence of salt during the film formation. The dependence on contact time and LbL film thickness on the critical pull-off force and work of adhesion are discussed. Specifically, by introducing sodium chloride (NaCl) in the assembly process, the pull-off forces can be increased by a factor of 10 and the work of adhesion by 2 orders of magnitude. Adjusting both the contact time and the film thickness enables control of the adhesive properties within these limits. Based on these results, we discuss how the fabrication procedure can create tailored adhesive interfaces with properties surpassing analogous systems found in nature.