S-scheme heterostructure can facilitate the separation of carriers while maintain outstanding redox capacity. A series of ternary Bi7O9I3/g-C3N4/Bi3O4Cl photocatalytic system was triumphantly synthesized via oil bath method in this work and used in photocatalytic degradation of phenol. The optimal TOC removal rate reached up to 93.57% under illumination for 160 min, which was slightly lower than phenol photodegradation (about 100%, 100 min). Correspondingly, the apparent rate constants for the decay of phenol are determined to be 0.0211 min-1. The experiment of free radical capture indicated that ·OH and ·O2- were the major oxidizing substances to degrade phenol. The products of phenol photodegradation were identified by high performance liquid chromatography (HPLC) and a possible degradation pathway was proposed. The characterization analysis and density functional theory (DFT) calculations demonstrated that dual S-scheme charge migration was generated at the interface of Bi7O9I3, g-C3N4 and Bi3O4Cl, contributing to an efficient separation of light-excited carriers. In the field of environmental remediation, the discovery of this work could open up promising vistas for designing bismuth-based ternary heterostructures with application potentiality.