A new approach for the fabrication of a multilayer film assembly is explored, which is based on the alternating assembling of poly(4-vinylpyridine) and poly(acrylic acid) via hydrogen bonding. The homogeneous multilayer films were characterized by UV-vis and X-ray diffraction measurements. The control of layer thickness was studied in detail via adjustment of the molecular weight and concentration of poly(4-vinylpyridine) solution. The nature of the interaction between the two polymers was identified as hydrogen bonding by IR spectroscopy.