A stable and high lubricant ultrathin film was fabricated by self-assembled procedure at room temperature. Thickness of the films was regularly increased with the layer-by-layer self-assembly process in which poly (acrylic acid)-ferric hydroxide (PAA-Fe(OH)3) sol as anion polyelectrolyte and photosensitive diazoresin (DR) as cationic polyelectrolyte. And the process which based on electrostatic attraction was verified by UV-vis measurement. Furthermore, the ionic bonds in the films converted to covalent bonds under UV irradiation. Finally, the surface morphology and microtribology of the films were investigated by atomic force microscopy (AFM) and friction force microscopy (FFM). The results indicate that the films are flat and uniform through the self-assembly technique and the surface friction coefficients maintain at a rather low value.