Iron-catalyzed oxidative cross-coupling of phenols offers a direct approach to the synthesis of complex phenol-based materials in an atom- and step-economic fashion. By acknowledging the possible pathways of the reaction, along with a profound understanding of the relevant mechanism, one can design a synthesis that will allow complete control over the regio-, chemo-, and stereoselectivity in a single synthetic step. Herein we suggest a mechanistic oriented approach towards the synthesis of unsymmetrical biphenols in a direct manner, without the need of pre-functionalization of the coupling partners prior the cross-coupling step.