A novel and efficient electrochemical method for electroselective and controlled cross-coupling of isoindolinones with equivalent alcohols has been developed without the need for metal catalysts and strong bases under mild conditions. The reaction provides a novel strategy for the controllable and effective synthesis of 3-alkoxyl and N-hydroxymethyl-substituted isoindolinones, which is adjusted by 4-OH-TEMPO and tolerates various substrates. This protocol is an efficient tool for the construction of C-O and C-N bonds with high chemoselectivity.