A photoinduced method for direct, site- and stereoselective glycosylation of native sugars is described. This approach bypasses the need for protecting groups and utilizes homolytic chemistry to generate a transient glycosyl donor, which undergoes radical-based cross-coupling with electrophiles upon light activation. The method enables the synthesis of a wide range of glycosyl compounds, including C-glycosyl, S-glycosyl, and Se-glycosyl derivatives, as well as O-glycosides, with high regio- and stereoselectivity. The strategy is also applicable for direct post-translational glycosylation of proteins, offering a biocompatible and efficient alternative to traditional methods. The process is based on a biomimetic approach inspired by natural S-glycosylation, where a thioglycoside intermediate is formed through regioselective anomeric phosphorylation, followed by stereoselective cross-coupling. The method avoids the need for complex protecting-group strategies, simplifying the synthesis of glycosyl compounds and enabling the direct functionalization of native sugars. The approach is demonstrated with various sugars and electrophiles, showing high efficiency and selectivity. The study highlights the potential of this method for the synthesis of complex glycans and glycoproteins, with applications in drug development and biological research.A photoinduced method for direct, site- and stereoselective glycosylation of native sugars is described. This approach bypasses the need for protecting groups and utilizes homolytic chemistry to generate a transient glycosyl donor, which undergoes radical-based cross-coupling with electrophiles upon light activation. The method enables the synthesis of a wide range of glycosyl compounds, including C-glycosyl, S-glycosyl, and Se-glycosyl derivatives, as well as O-glycosides, with high regio- and stereoselectivity. The strategy is also applicable for direct post-translational glycosylation of proteins, offering a biocompatible and efficient alternative to traditional methods. The process is based on a biomimetic approach inspired by natural S-glycosylation, where a thioglycoside intermediate is formed through regioselective anomeric phosphorylation, followed by stereoselective cross-coupling. The method avoids the need for complex protecting-group strategies, simplifying the synthesis of glycosyl compounds and enabling the direct functionalization of native sugars. The approach is demonstrated with various sugars and electrophiles, showing high efficiency and selectivity. The study highlights the potential of this method for the synthesis of complex glycans and glycoproteins, with applications in drug development and biological research.