The ordered multiplayer TiO2/Poly(DMCB) nanocomposite thin films were prepared by an evaporation-induced self-assembly method on a glass substrate. In the nanocomposite thin films, the surfactant DMCB was used as both structure-directing agents and monomers. The structures of the films were characterized using FTIR, XRD, and TEM. The results indicated that the films were composed of organic and inorganic layers with orderly interlaced arrangement and the interlayer distance between organic layer and inorganic layer was 7.17 and 6.26 nm before and after polymerization, respectively.