While hydrogen polysulfides (H<sub>2</sub>S<sub>n</sub>, n ≥ 2) are believed to play regulatory roles in biology, their fundamental chemistry and reactivity are still poorly understood. Compounds that can produce H<sub>2</sub>S<sub>n</sub> are useful tools. In this work we found that H<sub>2</sub>S<sub>2</sub> could be effectively produced from diacyl disulfide precursors, triggered by certain nucleophiles, in both aqueous solutions and organic solvents. This method was used to explore redox reactions of H<sub>2</sub>S<sub>2</sub>, such as scavenging 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and reduction of tetrazines.