The nonstoichiometric tetragonal Z-scheme Bi17-xGdxV3O33/Bi1.7-yGdyV8O16 fibers heterojunction was prepared by microwave hydrothermal method. It can be concluded that the initial strong alkaline environment can change the ions state from VO3- to V2O74- and VO43- including their connecting ways, generating tetragonal Bi17V3O33 and Bi1.7V8O16. The introduction of Gd3+ ions into the system resulted in surface dissolution, recrystallization, and the surface activity was adjusted. Finally, the Z-scheme Bi17-xGdxV3O33/Bi1.7-yGdyV8O16 fibers heterojunction photocatalyst was formed. Photocatalyst was proved to enhance the light absorption, carriers' migration abilities, and magnetic properties. Moreover, it improved the photocatalytic properties from 36.5% to 96.5% under UV light and was proved a promising photocatalysts.