In summary, an electrochemical strategy for the synthesis of alkylboronic esters from thioethers is presented. The paired electrolytic transformation tolerates a wide range of functional groups and was successfully applied to pharmaceutically relevant substrates and natural products. With the operational simplicity and scalable nature of this metal-free procedure, the method presents an attractive avenue to versatile products and demonstrates that thioethers are versatile precursors for cross-coupling transformations.