The xAl3+/BiVO4 (x = 0, 1%, 2%, 5%, 10%) photocatalysts were successfully prepared by hydrothermal method, and the removal efficiency of organic pollutants was improved in different degrees under the conditions of visible light irradiation. The results showed that proper Al3+-doping could improve the morphology of BiVO4, narrow the band gap and expand the absorption range of visible light. Meanwhile, Al3+ acted as a capture center for photogenerated electrons, reducing the recombination rate of the photogenerated electron-hole pair. When the doping amount of Al3+ was 1%, the photocatalytic activity was maximized, and the removal rate of RhB within 90 min was as high as 96%, this was an improvement of about 43% compared to pure BiVO4. In the whole reaction system, radO2-, h+ and radOH were the main active species, contributing 72.4%, 18.4% and 5.9% to the degradation of RhB, respectively.