Broadening the light absorption and inhibiting carrier's recombination are vital to the improvement of photocatalytic performance. Herein, self-assembly 3D hierarchical microsphere BiOIO3/Bi5O7I Z-scheme heterojunction with carrier transfer channel was firstly fabricated by in-situ solvothermal method. The degradation efficiency for bisphenol A (BPA) reached 98.9 % within 60 min visible light irradiation. The enhanced photocatalytic activity was benefited from the Z-scheme system assisted by iodate/iodide (IO3-/I-) as carrier transfer channel that not only accelerated the interfacial charge separation, but also provided massive reactive centers for obtaining high redox capacity. The vulnerable sites and the degradation pathways of BPA were identified by density functional theory calculations and liquid chromatography-mass spectrometry analyses. The toxicity of BPA and its intermediates were predicted by ECOlogical Structure Activity Relationship (ECOSAR) and the results demonstrated that BPA was eventually mineralized to harmless products. The Z-scheme charge transfer mechanism was deeply elucidated based on the role of active species (·O2-, ·OH and h+), band structure and carrier separation efficiency. This study provides a promising strategy for the photoactivity enhancement of bismuth based heterojunction in environment purification.