A selective dehydrogenative electrochemical functionalization of benzylic positions that employs 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP) has been developed. The electrogenerated products are versatile intermediates for subsequent functionalizations as they act as masked benzylic cations that can be easily activated. Herein, we report a sustainable, scalable, and reagent‐ and metal‐free dehydrogenative formal benzyl–aryl cross‐coupling. Liberation of the benzylic cation was accomplished through the use of acid. Valuable diarylmethanes are accessible in the presence of aromatic nucleophiles. The direct application of electricity enables a safe and environmentally benign chemical transformation as oxidizers are replaced by electrons. A broad variety of different substrates and nucleophiles can be employed.