A single semiconductor employed into photo(electro)catalysis is not sufficient for charge carrier separation. Designing a multiple heterojunction system is a practical method for photo(electro)catalysis. Herein, novel two-dimensional AgInS2/SnS2/RGO (AISR) photocatalysts with multiple junctions were prepared by a simple hydrothermal method. The synthesized AISR heterojunctions showed superior photoelectrochemical performance and photocatalytic degradation of norfloxacin, with a high degradation rate reaching 95%. More importantly, the toxicity of photocatalytic products decreased within the reaction process. High spatial separation efficiency of photogenerated electron-hole pairs was evidenced by optical and photoelectrochemical characterizations. Furthermore, a laser flash photolysis technique was carried on investigating the lifetime of the charge carrier of the fabricated dual heterostructures. In addition, sulfur and oxygen vacancies existed in AISR heterojunctions could largely constrain the recombination of electron-hole pairs. Density functional theory calculations were carried out to analyze the mechanism of photoinduced interfacial redox reactions, showing that reduced graphene oxide and AgInS2 act as electron and hole trappers in the photocatalytic reaction, respectively. Due to the interfacial electric field formed from AISR dual heterojunctions, the effective spatial charge separation and transfer contributed to the boosting photo(electro)catalytic performance.