A tetrabutylammonium tribromide-mediated three-component reaction of alkenes, diselenides, and sulfoximines has been established herein, providing direct and metal-free access to diverse β-arylseleno sulfoximine derivatives. This regioselective sulfoximido-selenization protocol proceeds efficiently under mild and ambient conditions with generally good yields. This strategy is featured by step and atom economy, practicability, a broad substrate scope, and gram-scale synthesis.