Construction of heterojunctions is conventionally regarded as the prevailing technique to enhance solardrivenphotocatalytic water splitting and photodegradation of pollutants. Herein, we report a noveldesign of a ternary Bi2O3/Bi/ZnIn2S4 system, which was facilely synthesized to satisfy these stringent criteriafor sunlight photocatalytic removal of organic and ionic pollutants and hydrogen evolution. Bi2O3/Bi/ZnIn2S4 could degrade 2,4-dinitrophenol (94.6%), tetracycline (96.5%), and Cr6+ (96.3%) effectivelyunder visible light and give a hydrogen production rate of 482.5 lmolg1h1 under visible light. Based on first-principles calculations and electrochemical results, our system could be identified as aZ-scheme. Photocorrosion of the sulfide is prohibited while the catalytic capabilities are simultaneouslybenefited due to lowered bandgap in light harvesting, internal electric fields in charge separations, andsurface plasmonic resonance enhanced electron boost.