Boron-doped diamond (BDD) electrodes provide an unusually wide electrochemical window in protic media, since there exist large offset potentials for the evolution of molecular hydrogen and oxygen, respectively. At the anode, alcohols are specifically converted to alkoxyl radicals. These can be used for chemical synthesis. When the enormous reactivity of such intermediate spin centers is not controlled, mineralization or electrochemical incineration dominates. Efficient strategies include either high substrate concentrations or fluorinated alcohols which seem to stabilize the spin centers in the course of reaction.