Two-photon solid-state fluorescence materials have received much attraction due to their wide optoelectronic applications. Herein, organic-inorganic hybrid two-photon fluorescence materials have been prepared by the introduction of a sulfonated stilbene (BSB, 4,4'-bis(2-sulfonatostyryl) biphenyl) assembled into layered double hydroxide (LDH) matrix. The structure and chemical composition of the composites were characterized by X-ray diffraction, elemental analysis, thermogravimetry and differential thermal analysis (TG-DTA). Fluorescence spectra demonstrate that the fluorescent properties (such as emission wavelength and photoluminescence quantum yield (PLQY)) of the as-obtained samples can be tuned by changing the layered charge density and chemical composition, in which the BSB/Zn3Al-LDH sample exhibited the highest emission intensity and PLQY. Moreover, the BSB/Zn3Al-LDH film was further fabricated by a solvent evaporation method, and the film exhibited well-defined one-photon and two-photon excited polarized photoemission with the anisotropy of ca. 0.12. It can be expected that these BSB/LDH systems can serve as a good candidate for new type of solid-state up-conversion and polarized fluorescent materials. (c) 2013 Elsevier B.V. All rights reserved.