Cationic starch (D.S. 0.065) and anionic starch (D.S. 0.037) were used to form biopolyelectrolyte multilayers. The influence of the solution concentration of NaCl on the adsorption of starch onto silicon oxide substrates and on the formation of multilayers was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). The wet adhesive properties of the starch multilayers were examined by measuring pull-off forces with the AFM colloidal probe technique. It was shown that polyelectrolyte multilayers (PEM) can be successfully constructed from cationic starch and anionic starch at electrolyte concentrations of 1 mM NaCl and 10 mM NaCl. The water content of the PEMs was approximately 80% at both electrolyte concentrations. However, the thickness of the PEMs formed at 10 mM NaCl was approximately twice the thickness formed at 1 mM NaCl. The viscoelastic properties of the starch PEMs, modeled as Voigt elements, were dependent on the polyelectrolyte that was adsorbed in the outermost layer. The PEMs appeared to be more rigid when capped by anionic starch than when capped by cationic starch. The wet adhesive pull-off forces increased with layer number and were also dependent on the polyelectrolyte adsorbed in the outermost layer. Thus, starch PEM treatment has a large potential for increasing the adhesive interaction between solid substrates to levels higher than can be reached by a single layer of cationic starch.