The composites of expanded graphite with TiO2 (EG/TiO2) were prepared in the method of impregnation, the morphology and crystal structure were characterized by the means of scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The decolorization performance of the EG/TiO2 composites for the methyl orange aqueous solution were studied. The experimental results were shown as follows: the EG/TiO2 composites maintained the porous and lamellar structure of EG, and a lot of anatase TiO2 particles as a small lump distributed on surfaces and in layers of EG. The composites may contain the graphite both oxidized and un-oxidized, and there was no other organic group left in the composites, except for the functional groups of graphite. Moreover, the EG/TiO2 composites had excellent decolorization performance for the methyl orange aqueous solution. When reacted for 90 min, the decolorization rate of the methyl orange aqueous solution was at the peak, up to 96.1%. We supposed that it was mainly due to the interaction between the strong adsorptive ability of EG and the degradation property of TiO2 particles.