A novel dot-like Cu2O-loaded TiO2/reduced graphene oxide (rGO) nanoheterojunction was synthesized via UV light reduction for the first time. Cu2O with size of ca. 5 nm was deposited on rGO sheet and TiO2 nanosheets. The products were characterized by infrared spectroscopy, Raman spectrum, UV-Vis diffuse reflectance spectra, XPS techniques, photoluminescence spectra. The results demonstrated that Cu2O and rGO enhanced the absorption for solar light, separation efficiency of electron-hole pairs, charge shuttle and transfer, and eventually improved photoelectrochemical and photocatalytic performance for contaminants degradation. The reaction time and anion precursor could affect the final copper-containing phase. As extending UV irradiation time, Cu2+ was be first reduced to Cu2O and then transformed to metal Cu. In comparison with CH3COO- (copper acetate), NO3- (copper nitrate) and Cl- (copper chloride), SO42- (copper sulfate) was the optimum for synthesizing pure Cu2O phase.