Carbon-sulfur-bridged glycomimetics were prepared by free radical hydrothiolation of the exocyclic double bond of unsaturated sugars. Reaction between benzoyl-substituted pyranoid-exoglycal and a range of thiols including peptide, 1-thioglycerol and 1-thiosugar derivatives gave β-D-configured carbon-sulfur-linked glycoconjugates with full stereoselectivity. Addition of a panel of thiols to a 3-exomethylene-glucofuranose derivative also proceeded in a stereoselective manner and afforded a series of D-allo-configured 3-deoxy-3-C-S-bridged glycoconjugates.