An azobispyridinium-bearing oligo-electrolytes linked with flexible alkyl chain was synthesized to use as a polycation. Layer-by-layer deposition between commercially available poly(sodium 4-styrene sulfonate) and oligomeric polycation with azobispyridine groups was successfully accomplished with electrostatic self-assembly technique, which was known to be a simple and versatile method for preparing supported multilayer thin films. It was found that the multilayers from layer-by-layer deposition process on hydrophilic glass slides and PET films could be fabricated with uniform thickness according to UV-Vis spectroscopy and ellipsometry. Surface topography of multilayer thin films were investigated by monitoring three dimensional images obtained by means of atomic force microscopy.