Corrosion and stress corrosion cracking of structural components cost an estimated $300 billion annually in the United States alone and are a safety concern for a number of industries using hot alkaline environments. These process environments may contain different amounts of sulfide and chloride; however, the combined role of these ions on the stress corrosion cracking of duplex stainless steels, which are widely used because of their generally reliable performance, had never been studied. This study shows that chlorides in sulfide-containing caustic environments actually have a significant influence on the performance of these alloys. A mechanism for stress corrosion cracking of duplex stainless steels in hot alkaline environments in the presence of sulfide and/or chloride was proposed. Microstructural and environmental aspects were studied using mechanical, electrochemical, and film characterization techniques. The results showed that selective corrosion of the austenite phase depended on percent sulfidity, alkalinity, and chloride content. Chlorides enhanced crack initiation and coalescence along the austenite/ferrite phase boundaries. Unstable passivity of duplex stainless steels in hot alkaline-sulfide environments was due to anion adsorption on the surface leading to defective film formation. Chlorides and sulfide available at the electrolyte/film surface reduced the charge transfer resistance and shifted the response of the films to lower frequencies indicating the films became more defective. The surface films consisted of an outer, discontinuous layer, and an inner, barrier layer. Fe, Mo, and Mn were selectively dissolved in alkaline and alkaline-sulfide environments. The onset of stress corrosion cracking was related to the extent of selective dissolution and was consistent with a film breakdown and repair mechanism similar to slip-step dissolution. Recommendations for reducing the susceptibility of duplex stainless steels to stress corrosion cracking in sulfide-containing caustic environments include reducing the chloride to hydroxide ratio and alloying with less Mo and Mn. The results will impact the petrochemical, pulp and paper, and other process industries as new duplex grades can be developed with optimal compositions and environments can be controlled to extend equipment life.