Herein, the metallic Bi-modified Bi3.84W0.16O6.24 hybrid with oxygen deficiencies is synthesized via a facile one-pot solvothermal reduction method. The synergistic effect of the deposited Bi metal and oxygen deficiencies results in the effective separation of the photogenerated carriers in Bi3.84W0.16O6.24 and the enhancement of the photo-response properties. As a result, Bi/Bi3.84W0.16O6.24 exhibited outstanding visible-light photocatalytic activities and sustained cycling performance. Under visible-light irradiation, nearly 96% of RhB is degraded after 15 min. Radical trapping experiments indicate that h(+) and (OH)-O-center dot are the main active species. This study provides an attractive avenue to design and fabricate highly efficient Bi-based photocatalysts, which possess a high application value in the field of environmental remediation, especially for wastewater purification.