The utilization of readily available starting materials to produce useful molecules is often challenged by selectivity issues. In this study, a Ni-catalyzed protecting-group-free C-C coupling protocol is described for the efficient synthesis of 2,2'-biphenol derivatives. Its remarkable chemoselectivity control ability, wide substrate scope, and excellent functional group tolerance highlight this newly developed strategy. Detailed mechanistic studies have demonstrated that potassium tert-butoxide acts as a critical agent to prevent the occurrence of protonation events.