A layered superlattice WO3/4,4＇-BAMBp self-assembled multilayer film has been fabricated onto aminopropylsilanated quartz or silicon substrate from transition-metal W compound and 4,4＇-BAMBp solution using a polyelectrolyte approach. The superlattice film showed good photochromic properties. UV-visible spectra were employed to study the growth process and the aggregation of organic molecules. A well-ordered superlattice structure was identified by X-ray diffraction. A possible structural model was proposed according to UV-visible, XRD, and XPS spectra.