The layer-by-layer (LBL) adsorption of polyelectrolytes onto charged surfaces from aqueous solutions produces multilayered surface structures. A multilayer film of polydiallyldimethylammonium chloride (PDDA) and polystyrenesulfonic acid, sodium salt (PSS), prepared using 1.0 M NaCl in the polymer solutions, has a vermiculate morphology with roughness greater than 30 nm. Atomic force microscopy (AFM) investigations show that the morphology of the films can be annealed by the introduction of salt solutions of various concentrations. Roughness measurements taken at various times after immersion in salt solution indicate that the decrease in surface roughness is consistent with second-order kinetics. A model is proposed to explain the morphology annealing that relies on the presence of salt ions that free up polymer-polymer contacts, allowing new ones to form. The formation of new polymer-polymer contacts results in a new film morphology.