The titanium dioxide (TiO(2)) nanorod-decorated graphene sheets photocatalysts with different TiO(2) nanorods population have been synthesized by a simple non-hydrolytic sol-gel approach. Electron microscopy and X-ray diffraction analysis indicated that the TiO(2) nanorods are well-dispersed and successfully anchored on the graphene sheet surface through the formation of covalent bonds between Ti and C atoms. The photocatalytic activities are evaluated in terms of the efficiencies of photodecomposition and adsorption of methylene blue (MB) in aqueous solution under visible-light irradiation. The as-synthesized TiO(2) nanorod-decorated graphene sheets showed unprecedented photodecomposition efficiency compared to the pristine TiO(2) nanorods and the commercial TiO(2) (P-25, Degussa) under visible-light. It is believed that this predominant photocatalytic activity is due to the synergistic contribution of both a retarded charge recombination rate caused by a high electronic mobility of graphene and an increased surface area originated from nanometer-sized TiO(2) nanorods. Furthermore, photoelectrochemical study is performed to give deep insights into the primary roles of graphene that determines the photocatalytic activity.