Photocatalytic technology has been widely studied because of using solar energy to degrade pollutants with high efficiency. However, rapid recombination of the photogenerated charges results in low efficiency and instability. In this study, a novel MIL-101(Fe)/Bi2WO6 heterojunction with high efficient for degradation of organic pollutants from wastewater under visible-light irradiation was synthesized. A 1O2 dominant Fenton assisted photocatalytic system was constructed by superimposing the photo-fenton effect of MIL-101(Fe) itself. The photocatalytic degradation efficiency of MIL-101(Fe)/Bi2WO6-3% heterojunction under visible light irradiation is 10.0 times that of Bi2WO6. Specifically, the designed MIL-101(Fe)/Bi2WO6 photocatalyst showed excellent organic degradation performance under visible light. The results of this work not only supply a novel angle to the design and develop Z-scheme heterojunction photocatalysts but also identify its vital application value in the field of environmental remediation.