HNbMoO6-based nanocomposite material T-HNbMoO6 is assembled by titania species dispersed on HNbMoO6nanosheets (N-HNbMoO6), which is obtained through the mechanical exfoliation of layered HNbMoO6 (L-HNbMoO6). The microstructures, skeleton features, and spectral-response characteristics of the as-prepared materials were characterized by means of technologies, such as powder x-ray diffraction, field emission scanning electron microscope with energy dispersive spectroscopy mapping, high-resolution transmission electron microscopy with energy dispersive x-ray spectrometer, N2 adsorption–desorption isotherms, laser Raman spectroscopy, x-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, Mott–Schottky curves, and H2 temperature-programmed reduction analysis. The photocatalytic activity was evaluated by the degradation of methylene blue dye under the Xe lamp irradiation. The results showed that the titania species are dispersed on the surface of N-HNbMoO6 resulting from the interaction between guest titania species and host N-HNbMoO6. T-HNbMoO6 owns the best photocatalytic performance, which may be attributed to the synergistic effect between N-HNbMoO6 and titania species.