The composites of expanded ghaphite with TiO2 (EG/TiO2) have been prepared in the method of precursor mixing, and the optimum preparation conditions have been studied. The morphology and crystal structure of the EG/TiO2 composites have been characterized by the means of SEM and XRD. Also their performance of decolorization for methyl orange solution has been researched. The results are shown as follows: the EG/TiO2 composites maintain the rich porous and network structure of EG, and a lot of anatase TiO2 particles widely distribute on surfaces and in layers of EG. Compared with TiO2 sol, taking tetrabutyl titanate as titanium source, the prepared EG/TiO2 composites have better performance. Increasing the added amount of tetrabutyl titanate, the decolorization rate of methyl orange solution increases at first, and then decreases. When adding 2 mL tetralbutyl titanate, the decolorization rate is at the peak, up to 98.4%. These results show the composites have excellent performance of decolorization for methyl orange solution. We suppose it is mainly due to the interaction between the adsorption of EG and the degradation of TiO2 particles.