Titanium dioxide (TiO2), one of semiconductor photocatalysts, has been widely used in the environmental remediation. However, due to its easy recombination of the electron–hole pair, the improvement to enhance TiO2 photocatalytic activity has been applied, such as coating with graphene oxide (GO). Here, a simple hydrolysis method was used to synthesize titanium dioxide/reduced graphene oxide (TiO2/rGO) hybrid. The hybrid is first synthesized by hydrolysis of titanium isopropoxide, and then annealed at 400 °C under flowing forming gas. The effects of various GO contents during the synthesis are investigated and the mass contents (8%, 15%, and 21%) of rGO in the hybrids are determined by thermogravimetric analysis. To compare with the TiO2 nanoparticles, the structures and morphologies of TiO2/rGO hybrids are characterized using XRD, TEM and SEM. The photocatalytic degradation of rhodamine B are studied under the illumination of solar simulation. All synthesized hybrids exhibit the superior photocatalytic activities than the bare TiO2, which shows rGO can contribute to reduce the electron-hole pair recombination. This method also provides a simple way to obtain graphene-based semiconductor composites as photocatalysts.