Herein, we disclose a facile photoinduced difunctionalization of alkenes, enabling the synthesis of valuable β-amino alcohols, β-amino ethers, and 1,2-diamines with diverse nucleophiles. The protocol relies on the use of readily accessible dibenzothiophene-based sulfilimines as novel N-radical precursors, showcasing high functional-group tolerance and exclusive regioselectivity under mild reaction conditions.