Abstract An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon‐heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B 2 pin 2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance. magnified image