The photoperoxidase microspheres Bi2WO6-Ni-DA@HRP were prepared by covalent binding under the action of electrostatic adsorption for the first time. It was achieved that horseradish peroxidase (HRP) was immobilized on the Bi2WO6via the self-polymerization of dopamine (DA). In this bio-photocatalytic system, the free radicals produced in situ on the surface of Bi2WO6 can activate HRP and induce the photo-enzyme synergistic catalysis function. The interfacial binding force between HRP and the photocatalyst significantly enhanced the electron conduction effect, which improved the separation efficiency and mobility of photogenerated electron-holes, and thus the catalytic effect was improved successfully. Compared with Bi2WO6 and free HRP, Bi2WO6-Ni-DA@HRP under no-added H2O2 have exhibited excellent catalytic activity for indole. The degradation efficiency reached 99.9 % for 20 mg·L−1 indole solution treated with Bi2WO6-Ni-DA@HRP for 210 min under visible light initiation. The free radical trapping experiment showed that holes (h+) and ·OH were the main active substances in the catalytic process. The photoperoxidase catalyst constructed in this study proposed a novel practical approach for the degradation of indole in water and significantly improved the application of HRP in water treatment.