AgI sensitized BiOI-Bi2O3 composite (AgI/BiOI-Bi2O3) with multi-heterojunctions was prepared using simple etching-deposition process. Different characterization techniques were performed to investigate the structural, optical and electrical properties of the as-prepared photocatalysts. It was found that the ternary Agl/BiOI-Bi2O3 composite exhibited: (1) improved photocurrent response, (2) smaller band gap, (3) greatly reduced charge transfer resistance and (4) negative shift of flat band potential, which finally led to easier generation and more efficient separation of photo-generated electron-hole pairs at the hetero-interfaces. Thus, for the reduction of Cr(VI), Agl/BiOI-Bi2O3 exhibited excellent photocatalytic activity under visible light irradiation at near neutral pH. AgI/BiOI-Bi2O3 was optimized when the initial molar ratio of KI to Bi2O3 and AgNO3 to Bi2O3 was 1:1 and 10%, respectively. The estimated k(Cr(VI)) on optimized Agl/BiOI-Bi2O3 was about 16 times that on pure Bi2O3. Good stability was also observed in cyclic runs, indicating that the current multi-heterostructured photocatalyst is highly desirable for the remediation of Cr(VI)-containing wastewater. (C) 2016 Elsevier B.V. All rights reserved.