Nonactivated alcohols along with arene compounds are used in electrochemical dehydroxylative arylation for constructing C(sp3)-C(sp2) bonds. The PIII reagent undergoes single-electron anodic oxidation to form its radical cation, which reacts with the alcohol to produce an alkoxytriphenylphosphine radical. Through spontaneous β-scission of the phosphoranyl radical, the C-O bond is cleaved to form an alkyl radical species, which couples with the radical anion generated by cathodic reduction of the electron-poor arene to afford the dehydroxylative arylated product.