A novel catalytic system for oxidative cross-coupling of readily oxidized phenols with poor nudeophilic phenolic partners based on an iron meso-tetraphenylporphyrin chloride (Fe[TP13] C1) complex in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) was developed. The unique chemoselectivity of this reaction is attributed to the coupling between a liberated phenoxyl radical with an iron-ligated phenolic coupling partner. The conditions are scalable for preparing a long list of unsymmetrical biphenols assembled from a less reactive phenolic unit substituted with alkyl or halide groups.