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), SO4
2− (copper sulfate) was the optimum for synthesizing pure Cu2O phase.Electronic supplementary materialThe online version of this article (doi:10.1007/s10853-017-0911-2) contains supplementary material, which is available to authorized users.