A chitosan/alginate dialdehyde multilayered film was fabricated using the layer-by-layer assembly method. Besides electrostatic interaction that promotes alternate adsorption of the oppositely charged polyelectrolytes, the Schiff base reaction between the amine groups on chitosan and the aldehyde groups on alginate dialdehyde provides a covalently cross-linked film, which after reduction by sodium cyanoborohydride is stable under both acidic and alkaline conditions. Moreover, the cross-linked film is responsive to changes in pH and addition of multivalent salts. The structural properties of the multilayered film such as thickness, refractive index, and water content were examined using simultaneous quartz crystal microbalance with dissipation monitoring and spectroscopic ellipsometry.