This article describes a novel, photoinduced approach to directly transform native sugars into complex saccharides without the need for protecting groups. The method involves site- and stereoselective chemical glycosylation using widely available native sugar building blocks, which are activated through homolytic chemistry to form transient glycosyl donors. These donors undergo radical-based cross-coupling with electrophiles under mild photoirradiation conditions, bypassing the need for complex protecting-group strategies. This 'cap and glycosylate' approach offers a straightforward method for synthesizing a wide array of metabolically robust glycosyl compounds, including C-glycosyl, S-glycosyl, and Se-glycosyl compounds, as well as O-glycosides. The method's biocompatibility allows for the direct post-translational glycosylation of proteins, providing a versatile platform for the synthesis of glycoproteins. The study highlights the efficiency, selectivity, and broad applicability of this approach in synthetic carbohydrate chemistry.This article describes a novel, photoinduced approach to directly transform native sugars into complex saccharides without the need for protecting groups. The method involves site- and stereoselective chemical glycosylation using widely available native sugar building blocks, which are activated through homolytic chemistry to form transient glycosyl donors. These donors undergo radical-based cross-coupling with electrophiles under mild photoirradiation conditions, bypassing the need for complex protecting-group strategies. This 'cap and glycosylate' approach offers a straightforward method for synthesizing a wide array of metabolically robust glycosyl compounds, including C-glycosyl, S-glycosyl, and Se-glycosyl compounds, as well as O-glycosides. The method's biocompatibility allows for the direct post-translational glycosylation of proteins, providing a versatile platform for the synthesis of glycoproteins. The study highlights the efficiency, selectivity, and broad applicability of this approach in synthetic carbohydrate chemistry.