A three-component oxychalcogenation reaction, from alkenes, diselenides/thiophenols, and H 2 O/alcohols, has been realized herein. Tetrabutylammonium tribromide (TBATB) and dimethylsulfoxide (DMSO) are utilized as the catalyst and the terminal oxidant, respectively, to enable this difunctionalization transformation. The metal-free reaction system shows good functional group compatibility, providing a unified and practical approach to access β-hydroxyl or β-alkoxy organochalcogenides.