Abstract To construct Z-scheme not only can effectively separate the excited electron-hole pairs, but also utilize the ample redox capability of each semiconductor component in this system for the surface photocatalytic reaction. In this work, a TiO2–Au–BiOBr ternary Z-scheme photocatalyst was constructed, in which Au NPs were used as the electron mediator to join BiOBr nanosheets and TiO2 nanofibers. The results showed that, under full spectrum irradiation, TiO2–Au–BiOBr nanofibers exhibited outstanding photocatalytic performance toward the degradation of Rhodamine B (RhB) with an excellent photodegradation efficiency of 99.91% within 30 min as well as good stability. The reaction mechanism of the TiO2–Au–BiOBr Z-scheme system was systemically studied by XPS, photoelectrochemical tests and free radical trapping experiments, etc. Moreover, the photocatalyst also exhibited excellent photocatalytic activity for degrading methyl orange and methylene blue.