We examined the assembly of the amine-rich polysaccharide chitosan from solution onto electrode surfaces as a result of voltage bias on the electrode. Chitosan is positively charged and water soluble under mildly acidic conditions and is uncharged and insoluble under basic conditions. We observed that chitosan is deposited from acidic solution onto the surface of a negative electrode and the thickness of the deposited layer is on the order of a micron. The thickness of the deposited layer was observed to be dependent upon the deposition time, the applied voltage, and the chitosan concentration. No deposition was observed on the positive electrode or on an “electrode” that had no applied voltage. Once deposited and neutralized, the chitosan layer can be retained on the electrode surface without the need for an applied voltage. Infrared (FT-IR) and electrospray mass spectrometry confirmed that the deposited material was chitosan. These results demonstrate that chitosan can be deposited and retained on elect...