A novel photocatalytic energy transfer-driven radical relay strategy has been introduced for the chemoselective and regioselective 1,4-difunctionalization of carbon-sulfur double bonds.This represents the first instance of radical-mediated dual-functionalization of X-Y type unsaturated bonds, enabling the synthesis of complex linear mols. with C-O, C-N, and C-S bonds in a single operation.The method surpasses traditional approaches by avoiding the need for thiourea intermediates and the harsh conditions typically associated with them.The developed strategy exemplifies versatility, being applicable to 1,4-oxyamination, 1,4-diamination, and 1,4-sulfonamination reactions, and has demonstrated compatibility with over 60 different substrates.The research also elucidates the role of electronic complementarity between radicals and receptors in achieving high selectivity in 1,4-difunctionalization reactions.This study significantly advances the field of bifunctionalization and remote difunctionalization reactions, with profound implications for the development of pharmaceuticals and materials science.