C(sp³)–H arylation has recently emerged as a powerful strategy involving new carbon–carbon bond formation for synthesizing complex organic molecules. We herein describe an efficient electrochemical C(sp³)–H arylation of xanthenes with arenes proceeding via a radical pathway. A series of 9-aryl-9H-xanthenes were observed to have been produced in the presence of a carbon anode, platinum cathode, MsOH and NHPI at room temperature from available N,N-disubstituted anilines, heterocyclic aromatic hydrocarbons and anisoles. Notably, the significant advantages of this transformation were found to include mild transition-metal-catalyst-free reaction conditions, good functional group tolerance, and a highly atom- and step-economic strategy.