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Although copper‐catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase‐type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl₂salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl₂in the presence of weakly coordinating tripodalN‐nitrosated ligandL^3NOhave been illustrated, while a closely related tripodal copper(II) complexL^3HCuCl₂(2) of the corresponding non‐nitrosated ligandL^3Hdoes not react with the phenolic substrates. Phenol reactions with CuCl₂in the presence of theL^3NOligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with ΔH^‡= 15.13 kcal mol⁻¹, ΔS^‡ = −9.6 eu, and kinetic isotope effectk₂(ArOH)/k₂(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl₂are capable of facilitating a proton‐coupled electron transfer (PCET) pathway.