A novel all-solid-state RGO/g-C3N4/BiVO4 Z-scheme heterostructure was prepared using a facile hydro-thermal method. The as-obtained RGO/g-C3N4/BiVO4 Z-scheme heterostructure exhibited enhanced photocatalytic activity toward the degradation of tetracycline hydrochloride under visible-light irradiation, which was about 1.13, 1.16, and 1.41 times higher than those of binary RGO/g-C3N4, g-C3N4/BiVO4, and RGO/BiVO4, respectively. The enhanced photocatalytic performance can be ascribed to the synergistic effect between the Z-scheme charge-carrier separation and RGO electron mediator, where RGO serves as a promoter for accelerating charge separation at the heterojunction, thus further leading to the improved photocatalytic activity. It is anticipated that the construction of RGO/g-C3N4/BiVO4 Z-scheme heterostructures is an effective strategy for the development of high-performance photocatalysts for the degradation of tetracycline hydrochloride.