Radical C-glycosylation presents a flexible and efficient method for synthesizing C-glycosides. Existing methods always require multistep processes for generating anomeric radicals. In this study, we introduce a streamlined approach to produce anomeric radicals through direct C-OH bond homolysis of unmodified saccharides, eliminating the need for protection, deprotection, or activation steps. These anomeric radicals selectively couple with activated alkenes, yielding C-glycosylation products with high stereoselectivity (>20:1). This method is applicable to a variety of native monosaccharides, such as l-arabinose, d-arabinose, d-xylose, l-xylose, d-galactose, β-d-glucose, α-d-glucose, and l-ribose, as well as oligosaccharides including α-lactose, d-(+)-melibiose, and acarbose. We also extend this approach to C-glycosylation of amino acid and peptide derivatives, and demonstrate a streamlined synthesis of an anti-inflammatory agent.