The series Ag-AgI/BiOI-Bi2O3 visible-light-driven photocataslyts were successfully synthesized by solvotherrnal method. The as-synthesized samples were systematically characterized by XRD, SEM, TEM, EDS, BET, XPS, FR-IR, UV-vis DRS, photoelectrochemical measurements and EPR. The formation mechanism of the new composite photocataslyts was investigated and the simulate formation process had been illustrated. The photocatalytic properties of the samples were evaluated by degradation of methyl orange under visible-light irradiation. The results shown that the 30% Ag-AgI/BiOI-Bi2O3 photocataslyts possessed the best photocatalytic activity and the kinetics reaction models were followed pseudo-first-order kinetics. The enhanced photocatalytic performance could be attributed to the effective separation and transfer of electron-hole pairs resulting by the deposing of Ag-AgI nanoparticles and Bi2O3. The photocatalytic mechanism was deduced by trapping experiments and EPR, and the results demonstrated that h(+), (OH)-O-center dot, O-center dot(2)- radicals played different roles in the degradation. Furthermore, a new Z-scheme multi-heterojunction mechanism was proposed basing on the results of trapping experiments and EPR.