Catalyst-free, direct electrooxidative phenol derivatives C(sp3)-H mono- and di-alkylation reaction have been developed. In contrast to previous typical oxidative and electrochemical coupling, this electrosynthetic approach enables selective mono- and di-alkylations through metal- and external oxidant-free mild conditions via easily available electrodes. Advances of this strategy were proven by an unparalleled broad substrate scope for efficient C-C, C-N, C-O bond formation as well as excellent site- and regioselectivity. The electrochemical se...