Precise structural control had attracted tremendous interest in nanosynthesis due to its great importance in tailoring the physical properties of nanomaterials. Here we report the synthesis of highly ordered CdS-Au-TiO2ternary Janus structure viatemplate-protected sequential growth and conversion method. Arising from the integration of the rectification effect of Au-CdS and Au-TiO2Schottky barriers, the Janus configuration of the CdS-TiO2domains, the plasmonic effect of Au nanosphere, and the Z-scheme charge transportation, the CdS-Au-TiO2Janus structure showed high efficiency in the model photocatalytic degradation of methyl orange (MO) dye. Importantly, the well-defined structural order allowed the identification of the correlation between the structure and the catalytic performance. We believe that the synthetic control and the mechanism insights would help the design and synthesis of sophisticated nanostructures, and would eventually promote their applications in photocatalysis fields.