Abstract A new protocol for the electrochemical synthesis of glycoconjugates is presented. Thioether derivatives of cholesterol and other sterols were subjected to anodic oxidation in the presence of a sugar alcohol affording glycoconjugates with the sugar linked to a steroid moiety by an ether bond. The isomeric 6β-3α, 5α-cyclo-steroidal thioethers proved to be better sterol donors than the normal 3β-Δ 5-steroidal thioethers.