A layered superlattice, WO3-polymer/1,10-decanediamine (1,10-DAD) self-assembled multilayer film, has been fabricated by means of alternating adsorption of transition metal tungsten compound and 1,10-DAD. UV-visible spectra were employed to study the growth process. The well ordered superlattice multilayer structure of WO3-polymer/1,10-DAD SAM film was identified by small angle X-ray diffraction (SAXRD) study. The d space of the SAM film was calculated as 2.897 nm from the SAXRD data, which agrees well with the results get by thickness measurement. The SAM film showed better photochromic properties compared with those of pre-reported WO3/4,4′-Bis(aminomethyl)-Biphenyl (4,4′-BAMBP) system. It's found that the exciting improved photochromic properties of WO3-polymer/1,10-DAD films come from the polymerization of WO3 molecules in the inorganic layers. The results clearly show that the organic molecules can efficiently manipulate the microstructure of the inorganic layer as well as the photochromic properties of the self-assembled multilayer films.