TiO2/Au/BDD composites with a Z-scheme structure was prepared by orderly depositing gold (Au) and titanium dioxide (TiO2) on the surface of a boron-doped diamond (BDD) film using sputtering and electrophoretic deposition methods. It was found that the introduction of Au between TiO2 and the BDD, not only could reduce their contact resistance, to increase the carrier transport efficiency, but also could improve the surface Hall mobility of the BDD electrode. Meanwhile, the designed Z-scheme structure provided a fast channel for the electrons and holes combination, to promote the effective separation of the electrons and holes produced in TiO2 and the BDD under photoirradiation. The electrochemical characterization elucidated that these modifications of the structure obviously enhanced the electrocatalytic performance of the electrode, which was further verified by the simulated wastewater degradation experiments with reactive brilliant red X-3B. In addition, it was also found that the photoirradiation effectively enhanced the pollution degradation efficiency of the modified electrode, especially for the TiO2/Au/BDD-30 electrode.