A simple, metal-free protocol for unsymmetrical biaryl coupling using H5IO6 is reported. H5IO6 was evaluated for a novel application in the oxidative cross-coupling of phenol-arene, phenol-phenol, and phenol-naphthol compounds. In this work, most of the couplings were completed within 30 min at ambient temperature. 30 coupling products were conveniently obtained using only 0.5 equivalent of H5IO6 in HFIP. A mechanism by which the transformation occurs is proposed.