Abstract: In order to investigate the preparation method and photocatalytic properties of composites comprised by reduced graphene oxide (RGO) and TiO₂ with high activity facets, RGO/nano TiO₂ composites were prepared by two-step hydrothermal method: the 1st step was the synthesis of nano TiO₂ exposed with high activity facets; the 2nd step was the recombination of as-synthesized nano TiO₂ and graphene oxide (GO), thus RGO/nano TiO₂ composites were formed. Then, the prepared nano TiO₂ with different exposed facets and RGO/nano TiO₂ composites were characterized by means of XRD, SEM, X-ray photoelectron spectrometer, ultraviolet-visible diffuse reflectance spectroscopy and so on, and the photocatalytic properties were evaluated. The results show that during the 1st step of hydrothermal method, nano TiO₂ which has high activity (001) and (101) facets can be controllably prepared by adjusting the concentration of HF. Fluorine atoms exist in nano TiO₂ by two states of physically adsorbing state and chemically binding state. After the 2nd step, GO recombines with nano TiO₂ to form RGO/nano TiO₂ composite, and GO is transformed to RGO simultaneously in the process. RGO/nano TiO₂ composites synthesized by two-step hydrothermal method have favorable photocatalytic performances under ultraviolet illumination, which outperform those of commercial TiO₂ (P25) and nano TiO₂. The photocatalytic properties of RGO/nano TiO₂ composites have remarkable improvement. RGO and exposed facets of TiO₂ have effects on the photocatalytic activity.