The layer-by-layer self-assembled NDR-PSS (nitro-containing diazoresin-polysodium p-styrenesulfonate) films were fabricated. The crosslinking structure formed from the conversion of ionic bond to covalent bond after UV irradiation, confirmed by small angle X-ray diffraction. The roughness and microtribological properties of NDR-PSS films were investigated by atomic force microscopy/friction force microscopy. The ordered multilayer films after photoreaction are better in microtribological performance than that of the monolayer film.