A process for fabricating graphene and TiO2 layer by layer composite was introduced to improve the photocatalytic activity by controlling the layers, thickness and the mass ratio between graphene and TiO2. The graphene oxide (GO) was synthesized from natural graphite powder by the modified Hummers method. Large-area uniform GO and TiO2 thin films were made by a spin-coating process in turn. After exposure of the TiO2/GO multilayer film to UV light irradiation which allows the reduction of GO to graphene, a novel photocatalytic structure as graphene and TiO2 layer by layer composite was synthesized. The cross-sectional SEM image showed that a clear layer by layer microstructure with a single layer thickness of graphene or TiO2 was in the range of about 50 nm. The total thickness of the film was around 5 μm which was varied according to the layer number of spin coating process. Raman spectra revealed that significant structural changes occurred through UV light irradiation. Photodegradation for methylene blue (MB) exhibited that the layer by layer composite is of higher photocatalytic activity than the pure TiO2 layer.