A NaCl-mediated electrochemical oxidation of amino acid carbamates (R1 = Boc, Cbz) afforded α-methoxylated α-amino acids. Subsequent acid-catalyzed elimination delivered valuable dehydroamino acid derivatives. The simplicity of our setup using graphite-electrodes was showcased, producing N-Boc-ΔAla-OMe on a decagram scale.