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AbstractThis work investigates a light‐driven 3‐component sulfonylation reaction of indolizines without needing any external photocatalyst. The mechanistic investigations support the formation of an electron donor–acceptor (EDA) complex in situ. This transformation offers a mild and sustainable approach with high functional group tolerance for the synthesis of 3‐sulfonylated indolizines. This compound class has valuable photophysical properties and represents promising candidates in various applications related to fluorescence.