A new type of TiO2 nanosheet-organic complex multilayer film was successfully prepared by the Langmuir-Blodgett technique. Surface pressure-area (pi -A) curves demonstrated that a stable monolayer of dioctadecyldimethylammonium bromide (DODAB) was formed on an aqueous suspension of TiO2 nanosheets derived from an exfoliated layered titanate, HxTi2-(x/4)square O-x/4(4).H2O (x similar to 0.7; square, vacancy). The hybrid monolayer of the ammonium amphiphiles and the TiO2 nanosheet was quantitatively transferred onto a hydrophobic quartz plate to form a multilayer film. X-ray diffraction measurements confirmed the formation of an ordered structure of DODAB/TiO2 with an interlayer distance of 3.4 nm.