Reduced graphene oxide supported titanium dioxide (GO/TiO2) heterojunction composites as highly active photocatalysts were synthesized via simple ultrasonic mixing and hydrothermal reaction using TiCl3 and GO as precursors. Their structure and morphology were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectra, UV-vis spectroscopy, and thermogravimetic analysis. The GO/TiO2 heterojunction composites were used to degrade methyl orange (MO). The adsorption and photocatalytic degradation rate of the prepared GO/TiO2 composites increased by nearly three times compared with that of pristine TiO2 or GO, which reached up 90%, to degrade MO after 4 h, which provides a simple method to obtain photocatalytic materials.